Studies in Surface Science and Catalysis 135
ZEOLITES AND MESOPOROUS MATERIALS AT THE DAWN OF THE 21 STCENTURY
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Studies in Surface Science and Catalysis Advisory Editors: B. Delmon and J.T. Yates Vol. 135
ZEOLITES AND M E S O P O R O U S M A T E R I A L S AT THE DAWN OF THE 21 sTC E N T U R Y Proceedings of the 13t" International Zeolite Conference, Montpellier, France, 8-13 July 2001
Edited by
A. Galarneau, F. Di Renzo and F. Fajula
Ecole Nationale Superieure de Chimie de Montpellier, 8 Rue de I'Ecole Normale, 34296 Montpellier Cedex 5, France
J. Vedrine
University of Liverpool, Leverhuime Centre for Innovative Catalysis, P.O. Box 147, Liverpool L69 3BX, U.K.
2001 ELSEVIER
Amsterdam - London - New York - Oxford - Paris - Shannon - Tokyo
ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 P.O. Box 211, 1000 AE Amsterdam, The Netherlands © 2001 Elsevier Science B.V. All rights reserved. This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery. Special rates are available for educational institutions that wish to make photocopies for non-profit educational classroom use. Permissions may be sought directly from Elsevier Science Global Rights Department, PO Box 800, Oxford OX5 1DX, UK; phone: (+44) 1865 843830, fax: (+44) 1865 853333, e-mail:
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Preface
The International Zeolite Conference is one of the pillars on which the identity of the zeolite community stands, at the same level of the definitions of zeolite structures provided by the Structure Commission of the International Zeolite Association, the dedicated journal which was Zeolites and is now Microporous and Mesoporous Materials, and the meetings of several national and regional zeolite associations. The 13th International Zeolite Conference has been held in Montpellier, France, from July 8 to 13, 2001, organized by the French Zeolite Group on behalf of the IZA. It has been preceded by a School on the Industrial Applications of Zeolites, held in Poitiers, and followed by a Field Trip in the natural zeolite localities of Massif Central. These proceedings are the expression of the oral and poster communications which have been presented during the Conference. They are subdivided into 32 thematic sessions going from the genesis of materials to their applications through their characterization. The paper volume contains the full texts of the 5 plenary and 6 keynote lectures and informative summaries of 150 oral and 540 poster presentations. It is intented to provide the participants a complete guide to the scientific programme. In order to gather all the communications in a handy document, the full texts of oral and poster presentations are available in a CD-ROM. These contributions have been selected among the 903 submissions received from a total of 57 countries! The evaluation was possible through the timely and efficient refereeing by the members of the International Advisory Board. The editors would like to namely acknowledge the dedication of the members of the Paper Selection Committee: Alberto Alberti, Giuseppe Bellussi, Colin Cundy, Jean-Pierre Gilson, Annick Goursot, Philip Llewellyn, Johann Martens, Jo~l Patarin, Cl6ment Sanchez, Alain Tuel and Herman van Bekkum. With the 13th IZC, zeolite science enters the new millennium with a vitality and an audience never reached before. Besides the fields of zeolite science always represented at IZCs (synthesis, characterization, catalysis .... ), some subjects strengthen their position (mesoporous materials, theory and modelling), new areas emerge (advanced materials, environmental and life sciences) and older ones regain interest (natural zeolites). The understanding and development of the unique properties of porous materials relies on a unique blend of multidisciplinary knowledge: material science, with the implication of organic and colloid chemistry, to prepare micro- and mesoporous materials, surface and adsorption science sustained by theory and modelling to understand the peculiar behavior of molecules in confined systems, special branches of catalysis, physics, chemical engineering and life science to design novel applications. The gathering of these elements is at the basis of a fruitful and evolutionary zeolite science, as it is hopefully reflected by these proceedings. Before concluding, the editors address a special and grateful acknowledgement to all the staff of the "Laboratoire de Mat6riaux Catalytiques et Catalyse en Chimie Organique" from Montpellier for their outstanding involvement all along the Conference organization.
vi
700
Papers published in IZC proceedings
600 -~ 500
~4oo Im
300 g~
200 100 0 Year
67
70
73
77
80
83
86
~...
89
.-
92 94 96 98 2001
v
-o, f f o
The vitality of zeolite community is witnessed by the trend of the contributions to International Zeolite Conferences.
Montpellier, April 12, 2001
Anne Galarneau
Francois Fajula
Francesco Di Renzo
Jacques V6drine
vii ORGANIZING COMMITTEE General Chairman Ecole Nationale Sul~rieure de Chimie de Montpellier, France Francois Fajula Scientific Chairman Jacques Vedrine University of Liverpool, UK Secretary Francesco Di Renzo Ecole Nationale Sup6rieure de Chimie de Montpellier,~France Treasurer Pascale Massiani
Universit6 Pierre et Marie Curie, Paris, France
Pre-Conference School Michel Guisnet Universit6 de Poitiers, France Jean-Pierre Gilson Universit6 de Caen, France Field Trip Subcommittee Philippe Rocher Service Gtologique Rtgional Auvergne, Clermont-Ferrand, France Alain Tuel Institut de Recherche sur la Catalyse, Villeurbanne, France Finance Jean-Pierre Gilson
Universit~ de Caen, France
Publications Anne Galarneau
Ecole Nationale Suptrieure de Chimie de Montpellier, France
Liaison to the IZA Council
Giuseppe Bellussi
EniTecnologie, San Donato Milanese, Italy
INTERNATIONAL ADVISORY BOARD Belgium
Janos B.Nagy Peter Jacobs Johan Martens Bulgaria Christo Minchev Canada Serge Kaliaguine China Da-Dong Li Zhongmin Liu
Faeultts N. D. de la Paix, Namur Katholieke Universiteit Leuven, Hevedee Katholieke Universiteit Leuven, Hevedee Bulgarian Academy of Sciences, Sofia Universit6 Laval, Quebec, Sainte Foy SINOPEC R/PP, Beijing Dalian Institute of Chemical Physics, Dalian
viii Jilin University, Changchun Ruren Xu Croatia Ruder Boskovic Institute, Zagreb Boris Subotic Cuba Gerardo Rodriguez Universidad de la Habana, Facultad de Fisica, La Habana -Fuentes Czech Republic Blanka Wichterlova J. Heyrovsky Institute of Physical Chemistry, Praha France Institut Lavoisier, Versailles G~rard Ferey Universit6 Pierre et Marie Curie, Paris Jacques Fraissard Ecole Nationale Sup6rieure de Chimie de Montpellier Annick Goursot Philippe Llewellyn Universit6 de Provence, Marseille Institut Fran~ais du P6trole, Rueil-Malmaison Alain M6thivier Ecole Nationale Sup6rieure de Chimie de Mulhouse Joel Patarin Universit6 Pierre et Marie Curie, Paris Cl6ment Sanchez TFE, Groupement de Recherches de Laeq, Lacq Jacques Tellier Georgia George Tsitsiehvili Georgian Academy of Sciences, Tbilisi Germany Institut far Anorganische Chemie, Hannover Peter Behrens Ludwig-Maximilians Universitat, Munchen Thomas Bein Wolfgang Hoelderich RWTH-Aachen, Aachen Fritz-Haber Inst. Max Plank Gesellschaft, Berlin Hellmut Karge Leipzig Fakultat for Physik und Geowissenschaften, Leipzig Jorg Karger Technische Universitat MOnchen Johannes Lercher Max Planck Institut ft~ Kohlenforshung, Muelheim Ferdi Sch0th Johannes Gutemberg Universitat, Mainz Klaus Unger Universitat Stuttgart Jens Weitl~mp Hungary Hungarian Academy of Sciences, Budapest Herman Beyer Hungarian Academy of Sciences, Budapest Denes Kallo Jozsef Attila University, Szeged Imre Kiricsi India National Chemical Laboratory, Pune Paul Ratnasamy Italy Universit~ di Perugia Alberto Alberti Giuseppe Bellussi EniTecnologie SpA, San Donato Milanese Universith di Salerno, Fisciano Paolo Ciambelli Universith di Napoli Federico II, Napoli Carmine Colella Universith di Torino Bite Fubini Universith di Torino Adriano Zecchina Japan Osaka Prefecture University, Osaka Mazakazu Anpo Daido Hoxan, Inc., Sakai, Osaka Tomoyuki Inui Mazakazu Iwamoto Tokyo Institute of Technology, Yokohama
Yoshio Ono Tokyo Institute of Technology, Yokohama Takashi Tatsumi Yokohama National University, Yokohama Osamu Terasaki Tohoku University, Sendai Tatsuki Yashima Tokyo Institute of Technology, Yokohama Korea Hakze Chon Korea Advanced Institute of Science and Technology, Taejon Ryong Ryoo Korea Advanced Institute of Science and Technology, Taejon Norway SINTEF, Oslo Michael Stocker New Zealand Neil Milestone Industrial Research Ltd, Lower Hutt The Netherlands Koos Jansen Delft University of Technology, Delft Thomas Maschmeyer Waterman Institute, Delft Herman van Bekkum Delft Unniversity of Technology, Delft Rutger van Santen Eindhoven University of Technology, Eindhoven Poland Miroslaw Derewinski Polish Academy of Sciences, Cracow Mafia Ziolek A. Mickiewicz University, Poznan Romania Emil Radu Russu ICERP SA, Ploiesti Russia Irina Ivanova Moscow State University, Moscow Leonid Kustov Russian Academy of Sciences, Moscow South Africa University of Capetown, Rondebosch Ciryl O'Connor Spain Avelino Corma Universidad Politecnica de Valencia Joaquim PerezPariente Instituto de Catalisis y Petroleoquimica CSIC, Madrid Switzerland Thomas Armbruster Universitat Bern Lynne Mc Cusker ETH Zarich Attain Pfenninger CU Chemie Uetikon AG, Uetikon Taiwan National Tsing Hua University, Hsinchu Kuei-Jtmg Chao United Kingdom Michael Anderson UMIST Chemistry Department, Manchester Royal Institution of Great Britain, London Richard Catlow Eric Coker BP Amoco Chemicals, Sunbury on Thames UMIST Chemistry Department, Manchester Colin Cundy Eric Derouane University of Liverpool USA John Armor Air Products & Chemicals Inc., PA - Allentown Kenneth Balkus Jr. University of Texas at Dallas, TX- Richardson David Bish Los Alamos National Laboratory, NM - Los Alamos
Anthony Cheetham University of California, CA- Santa Barbara University of California, CA- Santa Barbara Brad Chmelka California Institute of Technology, CA - Pasadena Mark Davis Dow Chemical Company, MI - Midland Juan Garces Dow Chemical Company, MI - Midland Charles Kresge SUNY - College at Brockport, NY - Brockport Fred Mumpton Alexandra Navrotsky University of California at Davis, CA - Davis Arizona State University, AZ - Tempe Michael O'Keeffe Thomas Pinnavaia Michigan State University, MI - East Lansing University of California, CA- Santa Barbara Galen Stucky Rose-Marie Szostak Georgia Institute of Technology, GA - Atlanta Robert Thompson Worcester Polytechnic Institute, MA - Worcester NEC Research Institute, NJ- Princeton Michael Treaty Pennsylvania State University, PA- University Park David Vaughan UOP, Inc., IL - Des Plaines Stephen Wilson Chevron Research & Tech. Co., CA- Richmond Stacey Zones
IZA COUNCIL President Jens Weitkamp
Universitat Stuttgart, Germany
Vice-President Cyril T. O'Connor
University of Capetown, Rondebosch, South Africa
Secretary Koos Jansen
Delft University of Technology, Delft, The Netherlands
Treasurer Rose-Marie Szostak Georgia Institute of Technology, GA - Atlanta, USA Members Giuseppe Bellussi Hakze Chon Tomoyuku Inui Hellmut G. Karge Johannes Lercher Johan A. Martens Lynne Me Cusker Michael St0cker Michael Treaty Ruren Xu Tatsuaki Yashima
EniTecnologie, San Donato Milanese, Italy Korea Advanced Institute of Science and Technology, Taejon, Korea Daido Hoxan, Inc., Sakai, Osaka, Japan Fritz-Haber Inst. Max Plank Gesellschaft, Berlin, Germany Technische Universitat M0nchen, Germany Katholieke Universiteit Leuven, Heverlee, Belgium ETH Z0rich, Switzerland SINTEF, Oslo, Norway NEC Research Institute, NJ - Princeton, USA Jilin University, Changchun, China Tokyo Institute of Technology, Tokyo, Japan
Support and Sponsoring (As of April 17, 2001) The Organizing Committee wishes to thank various institutions and companies for their financial support to IZC 13. Their contribution allowed a reduced registration fee for students and a bursary programme.
Institutions Minist&e de la Recherche CNRS R6gion Languedoc-Roussillon District de Montpellier Conseil G6n~ral de l'H&ault Universit~ Montpellier II Ecole Nationale Sup6rieure de Chimie de Montpellier St Nikon Foundation
Partners ExxonMobil TotalFinaElf UOP Institut Franqais du P6trole
Sponsors and Friends Air Liquide DSM Research Dow Chemicals EniTecnologie Grace Davison Haldor Topsoe Procatalyse Rhodia
xii
,,
Sessions
,,
,
List and schedule of sessions Oral ,
,,
Poster
01- Mineralogy of natural zeolites ......................................
Tuesday am
Tuesday pm
02- Zeolite nucleation and growth .......................................
Monday pm
Monday pm
03- New methods of zeolite synthesis ................................
Thursday pm
Thursday pm
04- Isomorphous substitutions ............................................
Friday am
Thursday pm
05- Synthesis of new materials ............................................
Tuesday pm
Tuesday pm
06- Fundamentals of micelle templating ..............................
Monday am
Monday pm Tuesday pm
07- New mesoporous molecular sieves ................................
Tuesday am
08- Syntheses with non-ionic surfactants ............................
Friday pm
Wednesday pm
09- Crystal structure determination .....................................
Wednesday am
Wednesday pm
10- Host-guest chemistry ....................................................
Monday am
Monday pm
11- Post-synthesis modification .........................................
Monday pm
Monday pm
12- In-situ spectroscopy and catalysis ...............................
Monday am
Monday pm
13- Frameworks and acid sites .............................................
Friday pm
Thursday pm
14- Frameworks, cations, clusters .......................................
Friday am
Thursday pm
15- Modelling and theoretical studies A ..............................
Tuesday am
Tuesday pm
16- Modelling and theoretical studies B ..............................
Tuesday pm
Tuesday pm
17- Principles of adsorption ................................................
Monday am
Monday pm
18- Adsorption and separation processes ...........................
Monday pm
Monday pm
19- Diffusion: fundamental approach ..................................
Tuesday pm
Tuesday pm
20- Zeolite membranes and films .........................................
Wednesday am
Wednesday pm
21- Nanoeomposite fundamentals and applications ............
Wednesday am
Wednesday pm
22- Advanced materials ........................................................
Thursday pm
Thursday pm
chemistry .............................................................................
Monday pm
Monday pm
24- New routes to hydrocarbon activation ..........................
Tuesday am
Tuesday pm
25- Conversion of aromatics ................................................
Tuesday pm
Tuesday pm
26- Catalysis for oil refining ................................................
Wednesday am
Wednesday pm
23- Micro- and mesoporous materials in fine
27- Selective oxidation and sulfur resistance .......................
Thursday pm
Thursday pm
28- Confinement and physical chemistry for catalysis .......
Friday am
Wednesday pm
29- New approaches to catalyst preparation ......................
Friday pm
Wednesday pm
30- Environmental catalysis .................................................
Friday am
Wednesday pm
31- Environment-friendly applications of zeolites...: .......... Friday pm
Thursday pm
32- Zeolite minerals and health sciences ..............................
Thursday pm
Thursday pm
xiii
Frequently a s k e d questions:
When do I have to present my oral communication? Look in the authors index section the code S-O-x corresponding to your communication(s) where S is the session number, 0 meaning oral and x the position of the communication, then refer to the previous page. Oral communications start in the morning at l Oh (except on Monday (l 0h30)) and in the afternoon at 16h30 and last 30 min each including 10 min discussion. -
When do I have to present my poster communication? Look in the authors index section the code S-P-x corresponding to your communication(s) where S is the session number, P meaning poster, then refer to the previous page. Poster communications are from 14h to 16h each day except on friday. Posters of the day session should be hanged during the morning coffee break (lOh-lOh30). -
Further details on the programme are provided in the following pages.
CONFERENCE PROGRAMME - -
13:OO
Lunch
Lunch
Lunch
Lunch
Lunch
13:30 A
14:OO
Poster1
14:30
Sessions
Poster III
Poster I1
29-0- 08-0- 31-0- 13-0-
Poster N
01
Exhibition
Sessions
Exhibition
Sessions
Exhibition
Sessions
Exhibition
02 15:OO 1930 16:OO
02 12 06 17 10 18 11 23 Coffee Break/Exhibition
16:30 23-K- 02-001 01 17:OO 23-0- 02-002 02 17:30 23-0- 02-003 03 18:OO 23-0- 02-00 4 0 4 18:30 23-0- 02-005 05
01 16 05 19 07 24 15 25 Coffee BreakExhibition
11-0- 18-0 25-0- 19-K- 16-0- 05-001
01
01
01
01
01
08 09 20 21
03 22 04 27 13 31 14 32 Coffee BreakExhibition
26 28 29 30
02
02
02
02
02-
11-0- 18-0 25-0- 19-0 16-0- 05-003
03
03
03
03
evening outing at
01 02
02
02
02
03
05 05 05. 2 1:00 CONCERT
03
03
0 4 0 4 0 4 0 4
27-0- 03-0- 22-0- 32-0,
05 05 05 05 20:OO CONFERENCE
DINER
NB: Keynotes (S-K-01) (grey) will begin 10 min before the start of oral sessions
03
01
02
02
02
29-0- 084- 31-0- 13-003
03
03
03
29-0- 08-0 31-0- 1343 0 4 0 4 0 4 0 4
Conciudiig Remarks
01
27-0- 03-0- 22-0- 32-0-
0 4 0 4 0 4 0 4 0 4 0 4 05
01
"MANADE Saint Gabriel" 27-0- 03-0- 22-0- 32-0-
03
ll-0- 18-0- 25-0- 19-0- 16-0 05-005
01
27-0- 03-0- 22-0- 32-0-
ll-0- 18-0- 25-0- 19-0 16-0 05-005
01
27-0- 03-K- 22-0- 32-0
16.30 Departure forthe
ll-0- 18-0- 25-0- 19-0- 16-0- 05-002
01
29-0- 084- 31-0- 13-0-
17:OO Departure to FIELD TRIP
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xvii
SCIENTIFIC PROGRAMME AND CONTENT OF PROCEEDINGS
Plenaries PL-1- Monday 9h - Ordered mesoporous materials - State of art and prospects F. Schiith PL-2- Tuesday 8h30 - Clinoptilolite-heulandite: applications and basic research T. Armbruster
13
PL-3- Wednesday 8h30 - Evolution of extra-large pore materials M.E. Davis
29
PL-4- Thursday 8h30 - Evolution of refining and petrochemicals. What is the place of zeolites? C. Marcilly
37
PL-5- Friday 8h30 - Is electron microscope an efficient magnifying glass for microand meso- porous materials? O. Terasaki and T. Oshuna
61
Note: The conference has been divided into 32 sessions. Each communication has a code S-M-x with S being the number of the Session, M = K (keynote), O (oral), P (poster) and x the number of the communication.
Keynotes 23-K-01- Monday 16h20- Delaminated zeolites as active catalysts for processing large molecules A. Corma and V. Forn~s
73
01-K-01- Tuesday 9h50 - Pentasil zeolites from Antartica: from mineralogy to zeolite science and technology A. Alberti, G. Cruciani, E. Galli, S. Merlino, 1~ Millmi, S. Quartieri, G. Vezzalini and S. Zanardi
83
19-K-01- Tuesday 16h20 - Use of 1H NMR imaging to study the diffusion and codiffusion of gaseous hydrocarbons in HZSM-5 catalysts P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L. Bonardet, J.-M. Dereppe and J. Fraissard
93
21-K-01- Wednesday 9h50 - Zeolite-based characterization and catalytic applications B. K Romanovsky
nanocomposites:
synthesis,
03-K-0 I- Thursday 16h20 - Application of combinatorial tools to the discovery and commercialization of microporous solids: facts and fiction J. Holmgren, D. Bem, M. Bricker, 1L Gillepsie, G. Lewis, D. Akporiaye, I. Dahl, A. Karlsson, A#..Plassen and R. Wendelbo
103
113
xviii
30-K-01- Friday 9h50 - The local structures o f transition metal oxides incorporated in zeolites and their unique photocatalytic properties
M. Anpo and S. Higashimoto
123
Note: In the b o o k are only the summaries o f the communications. The text o f the full papers o f oral and poster c o m m u n i c a t i o n s are in the C D - R O M . , Programme
o f o r a l s e s s i o n s (a~. lOh30-12h30 and pm 16h30-19h)
S u m m a r y pages
Monday am 12061017-
In-situ spectroscopy and catalysis .......................................................... F u n d a m e n t a l s o f micelle templating ........................................................ H o s t - g u e s t chemistry ............................................................................... PrinciPles o f a d s o r p t i 0 n ................. ... ....... .. ........................ .... . ..... ..,,.,: .....
133 134 135 137
Monday p m 23- Micro- and m e s o p o r o u s materials in fine chemistry ............................... 02- Zeolite nucleation and growth ................................................................. 11- Post-synthesis modification .................................................................... 18- Adsorptio n and separation processes .................................... ..:... .... ... .... ..
138 140 141 143
Tuesday am 24- N e w routes to hydrocarbon activation .................................................... 01- M i n e r a l o g y o f natural zeolites ................................................................ 15- M o d e l l i n g and theoretical studies A ........................................................ 07- N e w m e s o p o r 0 u s molecular sieves ..........................................................
145 146 148 150
Tuesday pm 25- Conversion o f aromatics .......................................................................... 19- Diffusion: fundamental approach ............................................................. 16- M o d e l l i n g and theoretical studies B ......................................................... 05- Synthesis .of n e w materials ............. ..:...:... ....... ......................................
151 153 155 156
Wednesday am 26212009-
Catalysis for oil refining .......................................................................... N a n o c o m p o s i t e fundamentals and applications ...................................... Zeolite m e m b r a n e s and films ................................................................... Crystal structure determination ...............................................................
158 160
161 163
Thursday pm 27032232-
Selective oxidation and sulfur resistance .................................................. N e w m e t h o d s o f zeolite synthesis ........................................................... A d v a n c e d materials .................................................................................. Zeolite minerals and health sciences ........................................................
165 166 168 170
Friday am 30280414-
E n v i r o n m e n t a l catalysis ........................................................................... C o n f i n e m e n t and physical chemistry for catalysis ................................. I s o m o r p h o u s substitutions ...................................................................... F r a m e w o r k s , cations , clusters ....... ::. ...... :..::...,.,,:. .................. :. ........ :.:;::..
171 173 175 176
Friday pm 29083113-
N e w a p p r o a c h e s to catalyst preparation ................................................ Syntheses with non-ionic surfactants ...................................................... Environment-friendly applications o f zeolites ........................................ F r a m e w o r k s and acid sites .......................................................................
178 179 181 182
xix
Posters should be hanged during the morning coffee break (1 Oh- 10h30).
Programme o f poster sessions (14h00-16h30)
,
Summary pages
Monday 0206101112171823-
Zeolite nucleation and growth ................................................................. Fundamentals o f micelle templating ........................................................ Host-guest chemistry ............................................................................... Post-synthesis modification .................................................................... In-situ spectroscopy and catalysis .......................................................... Principles o f adsorption ........................................................................... Adsorption and separation processes ...................................................... Micro- and mesoporous materials in fine chemistry ...............................
185 198 206 208 217 222 226 230
Tuesday 01- Mineralogy o f natural zeolites ................................................................ 05- Synthesis o f new materials ...................................................................... 07- N e w mesoporous molecular sieves .......................................................... 15- Modelling and theoretical studies A ........................................................ 16- Modelling and theoretical studies B ......................................................... 19- Diffusion: fundamental approach ............................................................ 24- N e w routes to hydrocarbon activation .................................................... 25- Conversion o f aromatics ..........................................................................
240 244 249 256 264 269 271 280
Wednesday 0809202126282930-
Syntheses with non-ionic surfactants ...................................................... Crystal structure determination ............................................................... Zeolite membranes and films ................................................................... Nanocomposite fundamentals and applications ...................................... Catalysis for oil refining .......................................................................... Confinement and physical chemistry for catalysis ................................. New approaches to catalyst preparation ................................................ Environmental catalysis ...........................................................................
284 288 291 296 301 307 311 320
Thursday 0304131422273132-
N e w methods o f zeolite synthesis ........................................................... Isomorphous substitutions ...................................................................... Frameworks and acid sites ....................................................................... Frameworks, cations, clusters .................................................................. Advanced materials .................................................................................. Selective oxidation and sulfur resistance .................................................. Environment-friendly applications o f zeolites ........................................ Zeolite minerals and health sciences ........................................................
330 335 340 347 359 365 369 373
AUTHOR INDEX
377
SUBJECT I N D E X
399
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xxi
F u l l p a p e r s (Texts included in the CD-ROM) O1 - M i n e r a l o g y
of Natural
Zeolite
0 1 - O - 0 2 - Natural zeolites mineralization in the Oligocene-Miocene volcanosedimentary succession of Central Sardinia (Italy) P. CappellettL G. Cerri, M. de Gennaro, A. Langella, S. Naitza, G. Padalino, M. Palomba and R. Rizzo
147
01-O-03 - C a t i o n location and its influence on the stability of clinoptilolite M.N. Johnson, G. Sankar, C.R.A. Catlow,. D. O'Connor, P. Barnes and D.Price
147
0 1 - O - 0 4 - The structure of Li-phillipsite A.F. Gualtieri
147
01-O-05 - Ion-exchange features of intermediate-silica sedimentary phillipsite C. Colella, E. Torracca, A. Colella, B. de Gennaro and D. Caputo and M. de Gennaro
148
0 l - P - 0 6 - Zeolites in impact craters M. V. Naumov
240
0 l - P - 0 7 - AI ordering in a dachiardite framework M. Kato and K. Itabashi
240
0 l-P-08 - Chemical composition and ion-exchange properties of a natrolite from Zahedan Region, Iran A.R. Sardashti, H. Kazemian and M. Akramzadeh Ardakani
240
0 l-P-09 - Physical, chemical and structural characterization of the volcanic tuff from the Maramures area, Romania R. Pode, G. Burtica, S. Herman, A. Iovi and 1. Calb
241
0 l-P-10 - Heulandite group zeolites from the Paleogene fresh water lake Blateshnitza Graben, Southwest Bulgaria Z. Milakovska, E. Djourova and R. Tzankarska
241
0 l-P-11 - Isodimorphism of templates in zeolites. New crystal chemistry of analcime and its analogues V. V. Bakakin
241
0 l-P-12 - Evaluation of clinoptilolite tuffs from Russia as ion exchangers using NH4 ions 1. V. Komarova, N.K. Galkina, V.A. Nikashina, B.G. Anfilov and K.I. Sheptovetzkaya
242
xxii 0 l-P-13 - Mineralogy, chemistry and ion-exchange properties of the zeolitized tufts from the Sheinovets caldera, E Rhodopes (South Bulgaria)
R. Ivanova, Y. Yanev, Tz. lliev, E. Koleva, T. Popova and N. Popov
242
0 l-P- 14 - Synthesis of titanium, niobium, and tantalum silicalite- 1 by microwave heating of the mixed oxide xerogel precursors
W.S. Ahn, K.Y. Kim, M.H. Kim and Y.S. Uh
242
0 l-P-15 - Different silver states stabilized in natural clinoptilolites
N. Bogdanchikova, B. Concepcion Rosabal, V. Petranovskii, M. Avalos-Borja and G. Rodriguez-Fuentes
243
0 l-P-16 - Physical-chemical and adsorptive properties of Armenia natural zeolites
F. Grigoryan, A. Hambartsumyan, tl. Haroyan and A. Karapetyan
243
0 l-P-17 - The sorption equilibria in natural zeolite-aqueous solutions systems
J. Perik, M. Trgo and S. Cerjan-Stefanovik
243
02 - Z e o l i t e N u c l e a t i o n a n d G r o w t h
02-0-01 - Small angle X-ray scattering on TPA-Silicalite-1 precursors in clear solutions: influence of silica source and cations
C.J.Y. Houssin, B.L. Mojet, C.E.A. Kirschhock, V. Buschmann, P.A. Jacobs, J.A. Martens and R.A. van Santen
140
02-0-02 - Nucleation processes in zeolite synthesis revealed through the use of different temperature-time profiles
C.S. Cundy, J.O. Forrest and R.J. Plaisted
140
02-0-03 - High yield synthesis of colloidal crystals of faujasite zeolites
Qinghua Li, D. Creaser and J. Sterte
140
02-0-04 - Colloid chemical properties of silicalite-1 nanoslabs
S. Kremer, C. Kirschhock, P. Rouxhet, PA. Jacobs and J.A. Martens
141
02-0-05 - Atomic force microscopy (AFM) used to relate surface topography growth mechanisms in SSZ-42
M. W. Anderson, N. Hanif J.R. Agger, C.-Y. Chen and S.I. Zones
141
02-P-06 - Epitaxial overgrowth of MAZ onto EMT type zeolite crystals
A.M. Goossens, V. Buschmann and J.A. Martens
185
02-P-07 - The transformation of zeolite A and X into nitrate cancrinite under low temperature hydrothermal reaction conditions
J. C. Buhl and C. Taake
185
xxiii 02-P-08 - Comparison of crystal linear growth rates for silicalite-1 in thermal and microwave syntheses C.S. Cundy and J. O. Forrest
185
02-P-09 - Effect of initial hydrogel milling on Na-ZSM-5 synthesis C. Falamaki, M. Edrissi and M. Sohrabi
186
0 2 - P - 1 0 - Synthesis and characterization of zeolite Z S M - 2 5 S.B. Hong, W.C. Paik, W.M. Lee, S.P. Kwon, C.-H. Shin, I.-S. Nam and B.-H. Ha
186
02-P-11 - A study on the crystallization of a lamellar aluminophosphate APO-M to a three-dimensional aluminophosphate APO-CJ3 K. Wang, J. Yu, Y. Song, Y. Zou and R. Xu
186
0 2 - P - 1 2 - S y n t h e s i s o f nanosized offretite crystals J. Hedlund and E. Kurpan
187
02-P-13 - Silicon oxide plays a driving role in the synthesis of microporous SAPO- 11 Z-Q. Liu and R. Xu
187
0 2 - P - 1 4 - S y n t h e s i s o f nanocrystal zeolite Y and its host effect H. Yang, R. L i, B. Fan and K. Xie
187
02-P-15 - Tailoring crystal size and morphology of zeolite ZSM-5 Ming Liu and S. Xiang
188
02-P-16 - Modeling of silicalite crystallization from clear solution K.A. Car&son, J. Warzywoda and A. Sacco, Jr.
188
02-P- 17 - Interaction/synergistic effect of Mg 2+ and Ba 2+ on the size and morphology of the zeolite L crystals S. Ferchiche, J. Warzywoda and A. Sacco, Jr.
188
0 2 - P - 1 8 - In-situ NMR study of mechanisms of zeolite A formation M. SmaihL S. Kallus and J.D.F. Ramsay
189
- E f f e c t s o f synthesis parameters on zeolite L crystallization Y.S. Ko, S.H. Chang and W.S. Ahn
189
0 2 - P - 2 0 - Some aspects of NU-86 zeolite crystallization S. V. Dudarev, A. V. Toktarev, G. V. Echevsky, C.L. Kibby and D.J. O'Rear
189
0 2 - P - 2 1 - S y n t h e s i s o f zeolite Sr, K-ZK-5 P.C. Russell S.L. Stuhler. A.L. Kouli, J. Warzywoda and A. Sacco, Jr.
190
02-P-19
xxiv 02-P-22 - Evidence for in-situ directing agent modification in zeolite syntheses J.C. Vartuli, G.J. Kennedy, B.A. Yoon and A. Malek
190
02-P-23 - The influence of different silica sources on the crystallization kinetics of zeolite Beta
W. Schmidt, A. E Toktarev, E Schath, K.G. lone and K. Unger
190
02-P-24 - Population balance: a powerful tool for the study of critical processes of zeolite crystallization
B. Subotic, T. Antonid and J. Bronik
191
02-P-25 - Synthesis of TMA-SOD from a novel type layered silicate by solid state transformation
Y. KiyozumL F. MizukamL Y. Akiyama, T. lkeda and T. Nishide
191
02-P-26 - Direct conversion of bulk-materials into MFI zeolites by a bulkmaterial dissolution technique
S. Shimizu and H. Hamada
191
02-P-27 - Synthesis of a new microporous silicate using DABCO-based structuredirecting agent
Y. Kubota, J. Pldvert, T. Honda, P. Wagner, M.E. Davis, T. Okubo, Ya. Goto, Y. Fukushima and Y. Sugi
192
02-P-28 - Heteroepitaxial connection of zeolites with different pore structures
T. Wakihara, J. Pldvert, S. Nair, M. Tsapatsis, S. Yamakita, Y. Ogawa, H. Komiyama, M. Yoshimura, M.E. Davis and T. Okubo
192
02-P-29 - Study of zeolite A crystallization from clear solution by hydrothermal synthesis and population balance simulation
J. Bronic, P. Frontera, E Testa, B. Subotic, R. Aiello and J. B.Nagy
192
02-P-30 - Synthesis of zeolite SSZ-35 using N-methyl hexahydrojulolidinium salt as a new family of structure-directing agents (SDAs)
Y Kurata, T.-A. Hanaoka and H Hamada
193
02-P-31 - The Fitting equation for zeolite crystallization with seeds
V. Toktarev and S. V. Dudarev
193
02-P-32 - Influence of the thermal treatment of the aluminosilicate gel precursor on the zeolite nucleation
C. Kosanovi~, B. SubotiO and D. Kralj"
193
02-P-33 - Efficient co-templating roles of amines and amides admixed with alkylammonium salts for the stabilisation of new A1PO4-n topologies
C. Borges, M.F. Ribeiro, C. Henriques, M.T. Duarte, J.P. Lourenqo and Z. Gabelica
194
XXV
02-P-34 - Static synthesis of zeolite M C M - 2 2 Y.-M. Wang, X.- T. Shu and M.- Y. He
194
02-P-35 - Synthesis of pure silica Beta by the conventional hydrothermal method W Guo, J. Yao, Y. Luo and Qi. Li
194
02-P-36 - Hydrothermal transformation of a layered silicate, Na-magadiite, into mordenite zeolite T. Selvam and W Schwieger
195
02-P-37 - In-situ diagnostic of zeolite crystal growth by real time ultrasound monitoring R. Herrmann, W Grill T.J. Kim, O. Scharf R. Schertlen, M. Schmachtl, W Schwieger, C. Stenzel, H. Toufar and Y. Venot
195
02-P-38 - Effect of ageing on the decomposition of tetra-alkylammonium ions as studied by microwave heating A. Arafat, H. van Bekkum, Th. Maschmeyer and J. C. Jansen
195
02-P-39 - Synthesis of siliceous mordenite from system free of amine X. Qi, X. Liu and Z Wang
196
02-P-40 - High-resolution solid state MAS NMR studies on the role of promoter (phosphate) in the nucleation and crystallization of Silicalite -1 (Si-MFI) P.R. Rajamohanan, P. Mukherjee, S. Ganapathy and R. Kumar
196
02-P-41 - The influence of concentration on the structure-directing effects of diethylenetriamine in the synthesis of porosils P. Behrens, V.J. Hufnagel and A.M. Schneider
196
0 2 - P - 4 2 - Synthesis of high-silica MWW zeolite L.M. Vtjurina, S.S. Khvoshchev and I. V. Karetina
197
03- New
Methods
of Zeolite
Synthesis
03-0-02- Mesoporous zeolites CJ.H. Jacobsen, J. Hou~,vicka, A. Carlsson and I. Schmidt
167
03-0-03 - Synthesis of novel zeolites SSZ-53 and SSZ-55 using organic templating agents derived from nitriles S.A. Elomari and S.I. Zones
167
03-0-04 - Synthesis of IFR-type zeolites optimized for spectroscopic study B.S. Duersch and L. W. Beck
167
xxvi 03-0-05 - Competitive role of sodium and potassium cations during hydrothermal zeolite crystallization from Na20-K20-A1203-SiO2-H20 gels A.F. Ojo, F.R. Fitch, M. Balow and M.-L. Lau
168
03-P-06 - Zeolitization of a spanish bentonite in seawater medium. Effect of alkaline concentration and time R. Ruiz, C. Blanco, C. Pesquera and E Gonz61ez
330
03-P-07 - Silicalite-1 spheres prepared from preformed resin-silicate composites L. Tosheva and J. Sterte
330.
03-P-08 - The synthesis of offretite single crystals using pyrocatechol as complex agent E Gao, G. Zhu, Xiaotian Li, S. Qiu, B. Wei, C. Shao and O. Terasaki
330
03-P-09 - Synthesis of FER type zeolite in presence of tetrahydrofuran G.-Q Guo, Y-J. Sun and Y.-C. Long
331
03-P- 10 - Utilization of dry-gel conversion method for the synthesis of gallosilicate zeolites Beta, ZSM-5 and ZSM- 12 R. Bandyopadhyay, Y. Kubota, S. i Nakata and Y. Sugi
331
03-P-11 - A novel method for the synthesis of cancrinite type zeolites C.F. Linares, S. Madriz, M.R. Goldwasser and C. Urbina de Navarro
331
03-P-12 - High-throughput strategies for the hydrothermal synthesis of zeolites and related materials N. Stock, N. Hilbrandt, K. Choi and T. Bein
332
03-P-13 - Static zeolite MCM-22 synthesis using two-level factorial design J. Warzywoda, S. Dumrul, S. Bazzana and A. Sacco, Jr.
332
03-P-14 - Influence of nano-particle agglomeration on the catalytic properties of MFI zeolite S. Inagaki, I. Matsunaga, E. Kikuchi and M. Matsukata
332
03-P-15 - Rapid and mass production of porous materials using a continuous microwave equipment D.S. Kim, J.M. Kim, J.-S. Chang and S.-E. Park
333
03-P- 16 - Hydrothermal synthesis of vanadium-containing microporous aluminophosphates via the design of experiments approach L. Frunza, P. Van Der Voort, E.F. Vansant, R.A. Schoonheyd and B.M. Weckhuysen
333
xxvii 03-P-17 - Synthesis of a thin Silicalite-1 membrane, through sintering, for use in a membrane reactor
E.E. McLeary, A. W. Hoogesteger, R.D. Sanderson and J.C. Jansen
333
03-P-18 - Mixed alkali templating in the Si/A1 = 3 and 10 systems: a combinatorial study
G.J Lewis, D.E. Akporiaye, D.S. Bem, C. Bratu,.I.M. Dahl, A. Karlsson, R.C. Murray, R.L. Patton, M. Plassen and R. Wendelbo
334
03-P-19 -Factors affecting composition and morphology of mordenite
F. Hamidi, M. Pamba, A. Bengueddach, F. Di Renzo and F. Fajula
334
04- Isomorphous Substitutions 04-0-01 - Direct synthesis of Cu(I)-MFI zeolite in the presence of Cu(II) methylamino complexes as mineralizing and reducing agents
S. Valange, F. Di Renzo, E. Garrone, F. Geobaldo, B. Onida and Z. Gabelica
175
04-0-02 - Preparation and catalytic properties of a novel type of zeolites with basic properties
S. Ernst, M. Hartmann and S. Sauerbeck
175
04-0-03 - Preparation and characterization of iron-substituted zeolites
G. Giordano, A. Katovic, A. Fonseca and J. B.Nagy
175
04-0-04 - Influence of the nature of T atoms on the morphology and crystal size of KZ-2 and ZSM-22 zeolites isomorphously substituted with AI or Fe
M. DerewihskL M. Kasture, J. Krydciak and M. Stachurska
176
04-0-05 - Synthesis and characterisation of novel large-pore vanadosilicates AM13 and AM-14
P. Brand6o, A. Philippou, N. Hanif, J. Rocha and M. Anderson
176
04-P-06 - Uniform distribution of nickel during the synthesis of Si-ZSM-5 through solid-state transformation
M. Salou, Y. Kiyozumi, E Mizukami, S. Niwa, M. lmamura and M. Haneda
335
04-P-07-Synthesis, characterization and catalytic activity of FeBEA and FeMFI zeolite obtained by xerogel wetness impregnation
O.A. Anunziata, L.B. Pierella, E.J. Lede and F.G. Requejo
335
04-P-08 - A novel method for the synthesis of chromium aluminosilicate with BEA structure
X.-H. Tang, L.-R. Pan, J.-Z. Wang and H. -X. Li
335
xxviii 04-P-09 - Pure SAPO, CoAPSO and ZnAPSO ATO-like molecular sieves through optimized synthesis procedures
A. Azzouz, N. Bflba, M. Attou, A. Zvolinschi and S. Asaftei
336
04-P-10 - Relation between amount of the niobium ammonium complex in the reaction mixture and the crystal size of an Nb- MFI zeolite
H. Munhoz Jr., S. Rodrigues," P.K. Kiyohara and W. Sano
336
04-P-11 - Spectroscopy of the formation of microporous transition-metal ion containing aluminophosphates under hydrothermal conditions
B.M. Weckhuysen, D. Baetens and R.A. Schoonheydt
336
04-P-12 - Co-templated synthesis of CrAPO-5 with various organic acids
J. Kornatowski, G. Zadrozna, J.A. Lercher and M. Rozwadowski
337
04-P-13 - How to increase the amount of framework Co 2+ in microporous crystalline aluminophosphates?
W. Fan, R.A. Schoonheydt and B.M. Weckhuysen
337
0 4 - P - 1 4 - Preparation of zinc containing zeolite catalysts
A. Katovic, E. Szymkowiak, G. Giordano, S. Kowalak, A. Fonseca and J. B.Nagy
337
04-P-15 - Synthesis of Zn and Fe substituted mordenite using citric acid as complexing agent
M. Dong, J.-G. Wang and Y.-H. Sun
338
04-P-16 - ET(Zr)S-4 molecular sieve' kinetic and morphological characterization
D. Vuono, P. De Luca, A. Fonseca, J. B.Nagy and A. Nastro
338
0 4 - P - 1 7 - Influence of alcali cations on the incorporation of iron into MFI structure in fluoride media
F. Testa, F. Crea, R. Aiello, K. L6zdr, P. Fejes, P. Lentz and J. B.Nagy
338
04-P-18 - Synthesis and characterization of Co-containing zeolites of MFI structure
E. Nigro, F. Testa, R. Aiello, P. Lentz, A. Fonseca, A. Oszko, P. Fejes, A. Kukovecz, I. Kiricsi and J. B.Nagy
339
05 - Synthesis of New Materials
05-0-01 - SOMS: Sandia Octahedral Molecular Sieves. A new class of ion exchangers selective for the removal of Sr 2÷ from waste streams
T.M. Nenoff M. Nyman, A. Tripathi, J.B. Parise, W.T.A. •Harrison and RS. Maxwell
156
xxix 05-0-02 - Hydrothermal synthesis of various titanium phosphates in the presence of organic amine templates Yunling Liu, Y. Fu, J. Chen, Y. Zou and W. Pang
157
05-0-03 - On the role of azamacrocycles and metal cations in the syntheses of metalloaluminophosphates STA-6,-7 a n d - 8 R. Garcia, E.F. Philp, A.M.Z Slawin, P.A. Wright and P.A. Cox
157
05-0-04 - Chiral transference and molecular recognition in novel Co(en)3Clatemplated zinc phosphates J. Yu, Yu Wang, Z Shi and R. Xu
157
05-0-05 - Very open microporous materials: from concept to reality A.K. Cheetham, H. Fjellvgtg, T.E. Gier, K.O. Kongshaug, K.P. Lillerud and G.D. Stucky
158
05-P-06 - Synthesis and structures of GIS, ABW and GME beryllophosphate molecular sieves from amine solutions H. Zhang, M. Chen, Z. Shi, Y. Zhou, Xin Xu and D. Zhao
244
05-P-07 - Microporous gallosilicate TNU materials and their implications for the synthesis of low-silica molecular sieves W.C. P a i l M.A. Camblor and S.B. Hong
244
05-P-08 - Synthesis and characterization of novel nickel phosphates from nonaqueous systems Yunling Liu, L. Zhang, P. Zhang, Y. Zou and W. Pang
244
05-P-09- Synthesis, characterization and properties of an anionic aluminophosphate molecular sieve with Br6nsted acidity W. Yan, J. Yu, R. Xu, Y. Han, K. Sugiyama and O. Terasaki
245
05-P-10 - Synthesis and characterization of an open-framework aluminophosphate [AIP206(OH)2][H30] containing propeller-like chiral motifs W Fan, J. gu, Z Shi and R. Xu
245
05-P-11 - Synthesis and characterization of an aluminum-substituted manganese phosphate with GIS topology H.-M. Yuan, Y.-S. Jiang, W. Chen, J.-S. Chen and R. Xu
245
05-P-12 - Synthesis and characterisation of novel microporous framework cerium and europium silicates D. Ananias, P. Ferreira, A. Ferreira, J. Rocha, J.P. Rainho, C.M. Morals and L.D. Carlos
246
xxx
05-P-13 - Novel microporous framework stannosilicates Z. Lin and J. Rocha
246
05-P- 14 - Magadiite intercalated M C M - 2 2 M. MunsignattL A.J.S. Mascarenhas, A.L.S. Marques and H. O. Pastore
246
05-P-15 - Synthesis of aluminum phosphite microporous materials N. Li and S. Xiang
247
0 5 - P - 1 6 - Synthesis, characterization and structural aspects of novel microporous indium L.M. King, J. Gisselquist, S.C. Koster, D.S. Bem, R.W. Broach, S.G. Song and R.L. Bedard
247
05-P-17 - Synthesis and characterization of the silicoaluminophosphate SAPO-47 L. Xu, Z. Liu, P. Tian, Y. Wei, C. Sun and ShL Li
247
05-P-18 - Synthesis, characterization and catalysis of SAPO-56 and MAPSO-56 molecular sieves P Tian, Z. Liu, L. Xu and C. Sun
248
05-P-19 - Synthesis and structural characterization of a novel microporous zeolitic type aluminium phosphate C. Sassoye, S. Girard, C. Mellot-Draznieks, T. Loiseau, C. Hugeunard, F. Taulelle and G. Fdrey
248
05-P-20 - Hydrothermal synthesis and crystal structures of two novel open frameworks: (enH2)3[Co3W4P4028] and (dapH2)3[Co3WnP4028] B. Yah, Y. Xu, N.K. Goh and L.S. Chia
248
06- Fundamentals
of Micelle Templating
06-0-01 - The effect of stoichiometry and synthesis conditions on the properties of mesoporous M41S family silicates W.J. Roth and J. C. Vartuli
134
06-0,02 - What are circular crystals? F. Marlow
134
06-0-03 - Hierarchically mesostructured zeolitic materials with the MFI structure D. Trong On, P. Reinert, L. Bonneviot and S. Kaliaguine
135
06-0-04 - Pore size engineering of MCM-48: The use of different additives as expanders M. Mathieu, E. Van Bavel, P Van Der Voort and E.E Vansant
135
xxxi 06-P-05 - X-ray diffraction analysis of ordered mesoporous silica M. Ookawa, Y. Yogoro, T. Yamaguchi and K. Kawamura
198
06-P-06 - Active MCM-48 supported catalysts: different strategies to increase the structural and chemical stability P. Van Der Voort, M. Mathieu and E.F. Vansant
198
06-P-07 - Strong acidic and high temperature hydrothermally stable mesoporous aluminosilicates with well-ordered hexagonal structure Zo. Zhang, Y. Han, R. Wang, S. Qiu, D. Zhao and F.-S. Xiao
198
06-P-08 - Studies on the synthesis of A I - l V I C M - 4 1 G.A. Eimer, L.B. Pierella and O.A. Anunziata
199
mesoporous materials
06-P-09 - Controlled synthesis of microporous and mesoporous silica-based molecular sieves in the presence of dodecyldimethylbenzylammonium chloride Z Y. Yuan, W. Zhou, L.M. Peng, J.-Z Wang and H.X. Li
199
06-P-10 - Formation of double-mesopore silica and its transformation into MCM-41 X.-Z. Wang, T. Dou, Y.-Z. Xiao and BI Zhong
199
06-P-11 - The synthesis and hydrothermal stability of directly usable hexagonal mesoporous silica by efficient primary amine template extraction in acidified water K. Cassiers, P. Van Der Voort and E.F. Vansant
200
06-P-12 - Synthesis and characterization of highly ordered chromium-substituted MCM-48 materials with tailored pore sizes C. Pak and G.L. Haller
200
06-P-13 - Preparation and characterisation of mesoporous silica spheres R. Van Grieken, D.P. Serrano, C. Martos and A.M. Melgares
200
06-P-14 - Rapid synthesis of high quality MCM-41 silica via ultrasound irradiation X.-H. Tang, Yanquing Wang, W Huang, S. Liu, O. Palchik, E. Sominski, Y. Koltypin and A. Gedanken
201
06-P-15 - Synthesis of mesoporous aluminosilicate FSM-materials derived from synthetic and natural Saponite T. Linssen, M. Barroudi, P. Cool and E.F. Vansant
201
06-P-16 - 129Xe NMR and adsorption studies of Si-MCM-48 and A1-MCM-48 G. Oye, M.-A. Springuel-Huet, J. Fraissard, M. StOcker and J. Sjoblom
201
xxxii 06-P-17 - 27A1.NMR studies on A1-MCM-41 molecular sieves synthesized with different Si/AI ratios and different aluminum sources
W. BOhlmann and D. Michel
202
06-P-18 - Control of formation of mesoporous SBA-3 and SBA-1 through organic additives
S. Che and T. Tatsumi
202
06-P-19 - The influence of A1, La or Ce in the thermal and hydrothermal properties of MCM-41 mesoporous solids
R.A.A. Melo and E.A. Urquieta-Gonzdlez
202
06-P-20- Controlling the assembly of silica mesoporous materials by varying the decrease in pH
J. Rathous~, J. Cejka, P.J. Kooyman, M. Slabovd and A. Zukal 06-P-21
-
203
Characterisation of MCM-41 aged for different periods
H. Al-Megren, T.-C Xiao, A.P.E. York, J. Sloan, S. Al-Khowaiter, S.-E Ji and ML.H. Green
203
06-P-22 - Synthesis and characterization of silica and aluminosilica-surfactant nanocomposites
E. Popovici, A. Visan, D. Filip, G. Burtica and R. Pode
203
06-P-23 - Improved thermal stability of mesoporous alumina support of catalysts for the isomerization of light paraffins
V. Gonzdlez-Peha, C. Mdrquez-Alvarez, E. Sastre and J. Pdrez-Pariente
204
06-P-24 - Synthesis of mesoporous molecular sieves MCM-48 under several reaction conditions
S. Rodrigues da Rocha and L. Domiciano Fernandes
204
06-P-25 - Parallel synthesis of mesostructured materials
P. Behrens and C. Tintemann
204
06-P-26 - Mesostructural transformation in the presence of fluoride anions
Q-H. Xia, K. Hidajat and S. Kawi
205
06-P-27 - Swelled Micelle-Templated Silicas (MTS): structure control and hydrophobic properties
D. Desplantier-Giscard, A. Galarneau, F. Di Renzo and F. Fajula
205
06-P-28 - Synthesis of pure and iron-containing mesoporous silica. Effect of washing and removal of template on the porous structure
L. Pasqua, E Testa, R. Aiello, E Di Renzo and E Fajula
205
xxxiii
07 - N e w M e s o p o r o u s M o l e c u l a r Sieves
07-0-01 - Ordered mesoporous carbon molecular sieves by templated synthesis: the structural varieties
R. Ryoo, S.H. Joo, S. Jun, T. Tsubakiyama and O. Terasaki
150
07-0-02 - One-pot synthesis of phenyl functionalized porous silicates with hexagonal and cubic symmetries
V. Goletto, M. Impdror and F. Babonneau
150
07-0-03 - State and redox behavior of iron in MCM-41
G. Pdl-Borb~ly, A. Szegedi, K. L6zdr and H.K. Beyer
150
07-0-04 - A comparative study of Cu interaction with niobium- and aluminumcontaining MCM-41 molecular sieves
M. Ziolek, I. Sobczak, I. Nowak, P. Decyk and J. Stoch
151
07-0-05 - A novel synthesis strategy leading to the formation of stable transitionmetal-oxide mesostructures
X.S. Zhao, J. Drennan and G.Q. Lu
151
07-P-06 - Vanadosilicate: Cubic mesoporous molecular sieve
M. Chatterjee, T. lwasaki, Y. Onodera, H. Hayashi, T. Ebina and T. Nagase
249
07-P-07 - Synthesis and characterization of mesoporous Cu-silica spheres via a novel co-assemble route
P. Zhang, N. Bai, X. Meng and W. Pang
249
07-P-08 - Synthesis and characterization of mesostructured alumina prepared in the presence of dodecylphosphate
L. Sicard, B. Lebeau, C. Marichal, J. Patarin and F. Kolenda
249
07-P-09 - Synthesis and characterizations of mesoporous zirconia-based oxide composites
J. Zha, D. Wu, Y.-H. Sun," Zh. Zhang, H. Zhang and D. Zhao
250
07-P-10 - Preparation and catalytic property of FeL/Y composite by a new method
B. Fan, W. Fan and R. L i
250
07-P-11 - Mesoporous zirconia: an anionic surfactant inorganic composite, precursor of a tridimensional porous material.
G. Pacheco and J.J. Fripiat
250
07-P-12 - Synthesis of micelle templated TiO2 mesophases by a sol-gel approach: effect of the surfactant removal
D.P. Serrano, G. Calleja, R. Sanz and P. Pizarro
251
xxxiv 07-P-13 - Preparation and characterization of iron oxide nanoparticles in the channels of MCM-41
C.M. Yang and K.J. Chao
251
07-P-14 - The evaluation of iron chromophore concentrations from iron containing MCM-41
C. Nenu, R. Ganea, R Bfrjega, Gr. Pop and M. Pitu
251
07-P-15 - Synthesis and characterization of the mesoporous material of single crystal particles
B. Lee, J. N. Kondo, D. Lu and K. i Domen
252
07-P-16 - Stabilization of uniformly sized and dispersed copper particles in new Cu-Zn-A1 mesoporous catalysts
S. Valange, J. Barrault, A. Derouault and Z. Gabelica
252
07-P-17 - A direct synthesis route to the mesoporous silicate SBA-2 bearing thiol groups
I. Diaz, F. Mohino, J. Pdrez-Pariente, E. Sastre, P.A. Wright and W. Zhou
252
07-P-18 - Template synthesis and characterisation of nanoporous alumina with narrow pore size distribution from inorganic salts
H. Y. Zhu, P. Cool G. Q. (Max) Lu and E. F Vansant
253
07-P-19 - Preparation and characterization of copper oxide modified MCM-41 molecular sieves
C. Minchev, R. KOhn, T. Tsoncheva, M. Dimitrov and M. Fr6ba
253
07-P-20 - Crystalline, mesoporous NiO-ZrO2-based solid oxide fuel cell catalysts
P. Ratnasamy, D. Srinivas, H.S. SonL A.J. Chandwadkar, H.S. Potdar, C.S. Gopinath and B.S. Rao
253
07-P-21 - Application of the AASBU method to the prediction of inorganic structures built exclusively of sodalite cages
S. Girard, P. PullumbL C. Mellot-Draznieks and G. F~rey
254
07-P-22 - Novel synthesis of nanoporous carbons using colloidal templates
S.B. Yoon, 1.S. Shin and J.-S. Yu
254
07-P-23 - Synthesis and characterization of mesoporous cerium silicate analogues of MCM-41 type molecular sieves
S. Laha, P. Mukherjee and R. Kumar
254
XXXV
07-P-24 - Synthesis of mesoporous materials using filtrate of alkali treatment of MFI zeolite M. Ogura, E. Kikuchi and M. Matsukata
255
08- Syntheses with Non-Ionic surfactants 08-0-01 - Mesoporous MSU-X silica tuned for filtration and chromatography applications C. Boissibre, A. Larbot and E. Prouzet
179
08-0-02 - Highly ordered mesoporous silicas synthesis using deca(oxyethylene) oleylether as surfactant: variation of the weight percentage of surfactant and incorporation of transition metal cations G. Herrier and B.-L. Su
180
08-0-03 - Silica walls of calcined mesostructured SBA-15 materials templated by triblock copolymers M. Imp&or and A. Davidson
180
08-0-04 - Template / AISBA-15 interaction: double resonance N M R study and consequences on structural properties J.-B. d'Espinose de la Caillerie, Y. Yue and A. Gdd~on
180
08-P-05 - The double-step synthesis of MSU-X silica: decoupling the assembly mechanism E. Prouzet, C. BoissiOre, N. Hovnanian and A. Larbot
284
08-P-06 - Steam - stable aluminosilicate MSU-S mesostructures assembled from zeolite seeds Yu Liu, W. Zhang and T.J. Pinnavaia
284
08-P-07 - A study on the mesoporous silica structures templated by triblock copolymers C.-P. Kao, H.-P. Lin, M.-C. Chao, H.-S. Sheu and C.-Y. Mou
284
08-P-08 - Study of methyl modified MSU-X silicas Y. Gong, Z Li, S. Wan, D. Wu, Y.-H. Sun, F. Deng, Q. Luo and }1. Yue
285
08-P-09 - Study of mesoporous materials with ultra high surface area prepared from alternate surfactants and silicate sources J. F. P~rez-Ardvalo, J.M. Dominguez, E. Terrds, A. Rojas-Herndndez and M. Miki
285
08-P-10 - Synthesis and catalytic properties of SO3H-mesoporous materials from gels containing non-ionic surfactants 1. Diaz, F. Mohino, E. Sastre and J. Pdrez-Pariente
285
xxxvi 08-P-11 - Secondary hydrolysis process to synthesize highly ordered mesoporous silica from nonionic surfactant with long hydrophilic chain J. Fan, C. Yu and D. Zhao
286
08-P-12 - Mesostructure design using mixture of nonionic amphiphilicblock copolymers J.M. Kim, S.-E. Park and G.D. Stucky
286
08-P-13 - Stability of mesoporous material SBA-15 and its benefit in catalytic performance C. Nie, L. Huang, D. Zhao and Q. Li
286
08-P-14 - Comparative study of the wall properties in highly-ordered silicate and aluminosilicate mesostructured materials of the MCM-41 and SBA-15 types L.A. Solovyov, V.B. Fenelonov, A. Yu. Derevyankin, A.N. Shmakov, E. Haddad, A. Gedeon, S.D. Kirik and V.N. Romannikov
287
09-Crystal Structure Determination 09-O-01 - Localisation of K + ions in (Na,K)-LSX and K-LSX zeolites by Rietveld analysis and 39KNMR spectroscopy. A new cationic site in the orthorhombic dehydrated K-LSX at room temperature J.L. Paillaud, P. Caullet, L. Delmotte, J.C. Mougenel, S. Kayiran and B. Lledos
163
09-0-02 - NMR crystallography of A1PO4-CJ2 F. Taulelle and C. Huguenard
163
09-0-03 - FOS-5, a novel zeotype with 3D interconnected 12- ring channels T. Conradsson, X. Zou and M.S. Dadachov
164
09-0-04 - Neutron diffraction study of protons in four lanthanum exchanged X and LSX zeolites D.H. Olson, B.H. Toby and B.A. Reisner
164
09-0-05 - Optimized synthesis and structural properties of lithosilicate RUB-29 So-Hyun Park, J.B. Parise and H. Gies
164
09-P-06 - Crystal structure of a cadmium sorption complex of dehydrated fully Cd(II)-exchanged zeolite X E. E Choi, S.H. Lee, Y.W. Han, E Kim and K. Serf
288
09-P-07 -The structure of a copper molybdate and its relation to other natural and synthetic porous materials based on transition metal polyhedra L. A. Palacio, A. Echavarria, A. Simon and C. Saldarriaga
288
xxxvii 09-P-08 - A 3-D open-framework nickel aluminophosphate [NiA1P2Os][C2N2H9]: assembly of 1-D AIP2083 chains through [NiOsN] octahedra B. Wei, Jihong Yu, Guangshan Zhu, F. Gao, Y. Li, R. Wang, Bo Gao, Xian. Xu, S. Qiu and O. Terasaki
288
09-P-09 - Structural modifications induced by high pressure in scolecite and heulandite: in-situ synchrotron X-ray powder diffraction study G. Vezzalini, S. Quartieri, A. Sani and D. Levy
289
09-P- 10 - Preparation, characterization, and crystal structures of fully indiumexchanged zeolite X N.H. Heo, S. W. Jung, S.W. Park J.S. Noh, W.T. Lim, M. Park and K. Serf
289
09-P-11 - Structural investigation by powder X-ray diffraction and solid state nuclear magnetic resonance of A1PO4-SOD M. Roux, C. Marichal, d.L. Paillaud, L. Vidal, C. Fernandez, C. Baerlocher and J.M. Chezeau
289
09-P-12 - Layered germanates with 9-membered rings X. Zou, T. Conradsson and M.S. Dadachov
290
09-P-13 - Dehydration dynamics of mordenite by in-situ time resolved synchrotron powder diffraction study: a comparison with electrostatic site energy calculations. A. Martucci, M. Sacerdoti and G. Cruciani
290
09-P-14 - Study of water vapor adsorption in the organically-lined channels of A1MepO-13 using X-ray powder diffraction K. Maeda, L.B. McCusker and C. Baerlocher
290
10- Host-Guest Chemistry 10-O-01 - Investigation of indium loaded zeolites and additionally promoted catalysts for selective catalytic reduction of NO× by methane F.-W. Schatze, H. Berndt, M. Richter, B. L~icke, C. Schmidt, T. Sowade and W. Granert
135
10-0-02 - Ion exchange of alkali metals and control of acidic/basic properties of MCM-22 and MCM-36 J.-O. Barth, R. Schenkel, J. Kornatowski and J.A. Lercher
136
10-0-03 - Insertion compounds of metal halides with porosils: "Structured Gases" P. Behrens, M. Hard, G. Wirnsberger, A. Popitsch and B. Pillep
136
xxxviii 10-0-04 - Site selective adsorption and catalytic properties of iron in FER and BEA zeolites Z Sobalik, J.E. Sponer, Z. Tvarfi~,kovd, A. Vondrovd, S. Kuriyavar and B. Wichterlovd
136
10-P-05 - Non-acidic zinc zeolite systems: preparation methods, formation processes and catalytic properties in dehydrogenation of methanol N. Ya. Usachev, E.P. Belanova, A. V. Kazakov, V.P. Kalinin, A.S. Fomin, 1.M. Krukovsky, G. V. Antoshin and O.K. Atal 'yah
206
10-P-06 - Incorporation of Ga ions into Y zeolites by reductive solid-state ion exchange R.M. MihdlyL H.K. Beyer and M. Keindl
206
10-P-07 - Heavy metal exchanged zeolites as precursors for high temperature stable phases W. Schmidt and C. Weidenthaler
206
10-P-08 - Preparation and characterization of H-ZSM-5 exchanged with cobalt by solid state ion exchange M. Mhamdi, S. Khaddar-Zine, A. Ghorbel, Y. Ben Taarit and C. Naccache
207
10-P-09 - Cyclic chemical vapour deposition of TEOS on ZSM-5: effect of deposition temperature on shape selective performance H. Manstein, K.P. Moller and C.T. O'Connor
207
11 - Post-synthesis Modification 11-O-01 - Gold-based mono- and bimetallic nanoparticles on HY zeolites G. Riahi, D. Guillemot, M. Polisset-Thfoin, D. Bonnin and J. Fraissard
141
11-O-02 - Unravelled from the back: kinetics of alkoxysilane CVD on zeolites and evidence for pore mouth plugging determined from model conversion over stepwise silanised samples H.P. ROger, H. Mantein, W. BOhringer, K.P. MOller and C.T. O'Connor
142
11-O-03-Templating role of F towards D4R units : study of the transformation of the fluorogallophosphate Mu-3 into Mu-2 A. Matijasic, P. Reinert, L. Josien, A. Simon and J. Patarin
142
11-O-04 - Modification of the Si/Ti ratio in ETS-10 G. Koermer, A. Thangaraj and S. Kuznicki
142
11-O-05 - Binuclear oxo-Fe species in Fe/ZSM-5 catalyst prepared by chemical vapour deposition P Marturano, L. Drozdovd, A. Kogelbauer and R. Prins
143
xxxix
1 l-P-06 - Dealumination of zeolite KL
E.E. Knyazeva, V.V. Yuschenko, F. Fajula and I.I. Ivanova
208
1 l-P-07 - Formation of acidic hydroxyl groups during preparation of Pt/KL catalysts as studied by ~H MAS NMR
T. Sato, S.-I. 1to, K. Kunimori and S. Hayashi
208
1 l-P-08 - Synthesis and characterization of mesopore Y Zeolite
B. Ma, W.F. Sun, Z.L. Sun and L.R. Chen
208
1 l-P-09 - Controlling the pore size of Hi3 zeolite by improved chemical vapor deposition of (CH3)3Si-O-Si(CH3)3
Y. Chun, X. Ye, Q.H. Xu and A.-Z. Yan
209
1 l-P- 10 - Influence of pH of the solution on realumination of BEA zeolite
Y. OumL R. Mizuno, K. Azuma, S. Sumiya, S. Nawata, T. Fukushima, T. Uozumi and T. Sano
209
1 l-P-11 - Formation of carbon-intercalated molybdenum sulfides
J.-S. Chen, Y. Wang, Y. Guo, Y. Zou and W. Xu
209
1 l-P- 12 - Characterization of partly-detemplated GaPO4-LTA
S.-F. Yu, C.-Y. Xi, H.-M. Yuan and J.-S. Chen
210
1 l-P-13 - Another study on the microwave heating of zeolite - without special loading materials
J. Dong, L. Xie, X. Jing, H. Xu, F. Wu and J. Hao
210
1 I-P-14 - Microwave plasma treatment as an effective technique for activation of zeolite catalysts
I.I. Lishchiner, O. V. Malova and E.G. Krasheninnikov
210
1 l-P-15 - Synthesis and characterization of microporous titanium-silicate materials
S. Mintova, B. Stein, J.M. Reder and T. Bein
211
1 l-P-16 - From borosilicate to gallo- and aluminosilicate zeolites: new methods for lattice substitution via post-synthetic treatment
C.Y. Chen and S. 1. Zones
211
1 l-P-17 - Studies on the structure of zeolite Y modified by radio-frequency fluorocarbon plasma treatment
S. Yamazaki, T. Nishimura, K. Furukawa, H. Ijiri and K. Tsutsumi
211
11-P-18 - Dual-temperature reagent-less ion-exchange separations on zeolites
V.D. Timofeevskaja, O.T. Gavlina, V.A. Ivanov and El. Gorshkov
212
1 l-P-19 - Rare earth exchange in small pore zeolites and its effect on their hydrothermal stability
G. Cao, M.J. Shah and W.A. Wachter
212
1 l-P-20 - Modification of mordenite and natural clinoptilolite by copper: role of drying temperature
I. Rodriguez-lznaga, V. Petranovskii, G. Rodriguez-Fuentes, N. Bogdanchikova and 3/1. Avalos
212
1 l-P-21 - Study on the acidity of modified HY zeolites prepared by combination of chemical dealumination and hydrothermal treatment
M. Han, L.-P Zhou, X.-W. Li and L.-Q. She
213
11-P-22 - Modification of Beta-zeolite by dealumination and realumination
J. Y. Zhang, L-P. Zhou and X. W. Li
213
11-P-23 - Ultrastable zeolites Y (USY) modified with phosphorus and boron
A. V. Abramova, Ye. V. Slivinsky, L. Ye. Kitaev, A.A. Kubasov, H. Lechert, W.D. Basler, V. V. Yushchenk and Z M. Matieva
213
11-P-24 - Structural properties and sieving effects of surface modified ZSM-5
S. Zheng, tl. Heydenrych, H.P. ROger, A. Jentys and J.A. Lercher
214
11-P-25 - The use of binary adsorption studies to investigate the effect of hydrothermal treatment on zeolites Rho and Mordenite
L.H. Callanan, C.T. O'Connor and E. van Steen
214
11-P-26 - Acid sites in thermal transformations of Ca-rich clinoptilolite
G.P. Valueva, I.S. Afanassiev, E.A. Paukshtis, Y.V. Seryotkin, N.K. Moroz and A.A. Budneva
214
11-P-27 - The effect of calcination on the isomorphously substituted microporous materials using ozone
D. Mehn, A. Kukovecz, I. Kiricsi, F. Testa, E. Nigro, R. Aiello, G. Daelen, P. Lentz, A. Fonseca and J. B.Nagy
215
11-P-28 - Alumination of siliceous zeolites
A. Omegna, M. Haouas, G. Pirngruber and R. Prins
215
11-P-29 - New hydrophobic Ti-Beta catalyst obtained by silylation and its catalytic performance for olefin epoxidation.
A. Corma, M.E. D6mine, J.A. Gaona, M.T. Navarro, F. Rey and S. Valencia.
215
1 l-P-30 - MFI zeolite with uniform mesopores created by alkali treatment
M. Ogura, E. Kikuchi and M. Matsukata
216
xli 12 - In-situ Spectroscopy and Catalysis 12-0-01 - 2D correlation IR spectroscopy of xylene isomerisation on H-MFI zeolite
F. Thibault-Starzyk, A. Vimont and J.-P. Gilson
133
12-O-02 - Structure/reactivity correlation in Fe/ZSM5 for deNOx applications. In-
situ XAFS characterization and catalysis A.A. Battiston, J.H. Bitter and D.C. Koningsberger
133
12-0-03 - Interaction of diazines with faujasites studied by IR spectroscopy, temperature-programmed desorption, and molecular modeling methods
J. DObler, E. Geidel, B. Hunger, K.H.L. Nulens and R.A. Schoonheydt
133
12-0-04 - DRIFT study of dinitrogen and dihydrogen adsorption on Li- and Naforms of LSX zeolite
V.B. Kazansky, A.I. Serykh, E. Tichomirova, V. Yu Borovkov and M. Bulow
134
12-P-05 - Study of relationship between mordenite acidity and structure with calcination temperature
Z. Zhu, Q. Chen and We. Chen
217
12-P-06 - Infrared observation of the stable carbenium ions formed by adsorption of olefins on zeolite Y at low temperatures
S. Yang, J.N. Kondo and K. Domen
217
12-P-07 - Characterization of aluminosilicate zeolites by UV-Raman spectroscopy
Y. Yu, G. Xiong, C. Li and F.-S. Xiao
217
12-P-08 - Adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on sodiumion exchanged faujasites with different Si/A1 ratios
1.A. Beta, H. BOhlig, J. DObler, H. Jobic, E. Geidel and B. Hunger
218
12-P-09 - DRIFT and FTIR spectra of N2 and C2H4adsorbed on CuNaY
G. Habner and E. Roduner
218
12-P-10 - Raman study of the building units in the zeolite structure
P.P.H.J.M. Knops-Gerrits, X.-Y. Li, N.-T. Yu and P.A. Jacobs
218
12-P-11 - Positron annihilation study in MCM-41
1t. Y. Zhang, Y.J. He, Y.B. Chen, H.Y. Wang and T. Horiuchi
219
12-P-12 - N M R studies on the pyrrole adsorption over Na +, Li + exchanged zeolites of type FAU
M. Sdlnchez-S6nchez and T. Blasco
219
xlii 12-P-13 - Variable-temperature FTIR study of the equilibrium between C-bonded and O-bonded carbon monoxide in H-ZSM-5 G. Turnes Palomino, M. Peharroya Mentruit, A.A. Tsyganenko, E. Escalona Platero and C. Otero Aredn
219
12-P-14 - Role of the various acid sites in MOR on o-xylene conversion: An insitu I.R. approach O. Marie, F. Thibault-Starzyk, P. Massiani and J.C. Lavalley
220
12-P-15 - FTIR- Studies on adsorption and decomposition of NO on in-situ synthesized ZSM-5/cordierite catalysts N. Guan, X. Shan, X. Zeng, S. Xiang, A. Trunschke and M. Baerns
220
12-P-16 - Acid sites in dealuminated mordenite V.L. Zholobenko and G.P. Mitchell
220
12-P-17 - Infrared study of iron-exchanged Y zeolite and its HDS activity M Nagai, O. Uchino and S. Omi
221
13 - F r a m e w o r k s and Acid Sites 13-0-01 - Where are the acid sites in zeolites? A novel NMR approach to measure B/A1 ordering around structure directing agents H. Koller, M. Kalwei, C. Fild, R.F. Lobo, MA. Camblor, L.A. Villaescusa and L. van W~illen
182
1 3 - 0 - 0 2 - The effect of the nature of heteroatoms (A1, Fe, B) on their distribution in the ZSM-5 structure J. D~degek, M. Tudor and J. (~ejka
182
13-0-03 - Toward the quantification of aluminum in zeolites using highresolution solid-state NMR C. Fernandez, A.-A. Quoineaud, V. Montouillout, S. Gautier and S. Lacombe
183
13-0-04 - Acidity of ITQ-2 zeolite as studied by FT-IR spectroscopy of adsorbed molecules in comparison with that of MCM-22 B. Onida, F. Geobaldo, L. Borello and E. Garrone
183
13-P-05 - In-situ FTIR studies of the acidity of H3PWl2040 and its porous salts. Interaction with H20, NH3 and pyridine N. Essayem, A. Holmqvist, G. Sapaly, J.C. V~drine and Y. Ben Tdarit
340
13-P-06 - Dynamics of p-nitroaniline in the micropore of zeolite ZSM-5 studied by solid-state N M R S. Hayashi and Y. Komori
340
xliii 13-P-07 - The use of microcalorimetry to study the effects of post-synthesis treatments on the modification of the acidity of several HY-type zeolites A. Auroux and M.L. Occelli
340
13-P-08 - ESR investigations of the catalytic properties of Lewis acid sites in Hmordenite T.M. Leu and E. Roduner
341
13-P-09 - External surface acidity of modified zeolites: ESR via adsorption of stable nitroxyl radicals and IR spectroscopy A.B. Ayupov, G.V. Echevsky, E.A. Paukshtis, D.J. O'Rear and C.L. Kibby
341
13-P-10 - Very strong acid site in HZSM-5 formed during the template removal step; its control, structure and catalytic activity A. Kohara, N. Katada and M. Niwa
341
13-P-11- Correlation between liB NMR isotropic chemical shifts and structural parameters in borates and boro-silicates J. Pl~vert, F. Di Renzo and F. Fajula
342
13-P-12 - Investigation of the paramagnetic effect of oxygen in the Z3Na MAS NMR and 23Na MQMAS NMR spectra of LiNaX R.J. Accardi, M. Kalwei and R.F. Lobo
342
13-P-13 - Characterization of acidic sites in HY and LaY zeolites by laserinduced fluorescence of adsorbed quinoline A. Lassoued, J. Thoret, P. Batamack, A. Gdddon and J. Fraissard
342
13-P- 14 - Dynamic behaviour of acetonitrile molecules adsorbed in ALPO4-5 and SAPO-5 studied by solid NMR method S. lshimaru, M. lchikawa, K. Gotoh and R. lkeda
343
13-P-15 - Determination of the Si/A1 ratio of faujasite-type zeolites C.H. Rascher, J.-C. Buhl and W. Lutz
343
13-P-16 - Theoretical investigation of the chemical shift anisotropy of toluene adsorbed on zeolite X A. Simperler, A. Philippou, D.-P. Luigi, R.G. Bell and M. W. Anderson
343
13-P-17 - Acid properties of dexydroxylated ferrierites studied by IR spectroscopy J. Datka, B. Gil and K. G6ra-Marek
344
13-P-18 - Aluminium species in activated zeolites: solid-state NMR spectroscopy of the active sites B.H. Wouters, T.-H. Chen and P.J. Grobet
344
xliv
13-P-19 - Aluminium distribution in high silica pentasil ring zeolites B. Wichterlovd, J. Dgdedek, Z Sobalik and J. Cejka
344
13-P-20 - Effects of hydration on A1PO4-14 and AIPO4-18 structures: 31p MAS and 27A1 3Q-MAS NMR study
C. V. Satyanarayana, R. Gupta, K. Damodaran, S. Sivasanker and S. Ganapathy
345
13-P-21 - Comparative study of the acidity of the structurally related faujasite type zeolites: FAU, EMT and ZSM-20
H. Kosslick, R. Fricke, H. Miessner, D.L. Hoang and W. Storeck
345
13-P-22 - The effect of flexible lattice aluminum in zeolites during the nitration of aromatics
M. Haouas, A. Kogelbauer and R. Prins
345
13-P-23 - Characterization of acidic sites in zeolites by heteronuclear double resonance solid state NMR
S.B. Waghmode, A. Abraham, S. Sivasanker, J.P. Amoureux and S. Ganapathy
346
13-P-24 - Measurement of MQMAS heteronuclear correlation spectra in microporous aluminophosphates
C. Fernandez and M. Pruski
346
13-P-25 - FTIR studies of the interaction of aromatic and branched aliphatic compounds with internal, external and extraframework sites of MFI-type zeolite materials
7". Armaroli, A. Guti~rrez Alejandre, M. Bevilacqua, M. Trombetta, F. Milella, J. Ramirez and G. Busca
346
14- Frameworks, Cations, Clusters 14-0-01 - Imaging the mesopores in zeolite Y using three-dimensional transmission electron microscopy
A.H. Janssen, A.J. Koster and K.P. de Jong
176
14-O-02 - 170 NMR studies of the structure and basic properties of zeolites
D. Freude, T. Loeser and U. Pingel
177
14-0-03 - Theoretical interpretation of UV-VIS spectra of Cu- and Ag-species in zeolites: structure vs. transition energies.
P. Nachtigall, M. Davidov6, M. Silhan and D. Nachtigallovd
177
14-0-04 - Silver ions and quantum-sized silver sulfide clusters in zeolite A D. Brtihwiler, C. Leiggener and G. Calzaferri
177
xlv 14-O-05 - Elucidating the nature and reactivity of cobalt ions in CoAPOs. A combined FTIR and EPR study of NO and NO2 adsorbed at 77 K and 298 K
E. Gianotti, M.C. PaganinL G. Martra, E. Giamello, S. Coluccia and L. Marchese
178
14-P-06 - Relaxation processes of Na ion in dehydrated Nal2-A zeolite
T. Ohgushi and K. Ishimaru
347
14-P-07 - Adsorption of DTBN at monovalent cations in zeolite y as studied by electron spin resonance spectroscopy
M. Gutjahr, W. BOhlmann, R. BOttcher and A. POppl
347
14-P-08 - Nature of the active sites of Mo-containing zeolites. XANES studies at Mo K and LIH-edges
F.G. Requejo, E.J. Lede, L.B. Pierella and O.A. Anunziata
347
14-P-09 - EPR studies on nitrogen monoxide in zeolites
H. Yahiro, N.P. Benetis, A. Lund and M. Shiotani
348
14-P-10 - Evidence of partially broken bridging hydroxyls in molecular sieves from IH MAS spin echo NMR spectroscopy
T.-H. Chen, B.H. Wouters and P.J. Grobet
348
14-P-11 - Structure change of molecular sieve SAPO-37 at high temperature studied by 27A1 MQ MAS NMR
T.-H. Chen, B. Wouters and P. Grobet
348
14-P-12 - Effects of molecular confinement on structure and catalytic behaviour of metal phthalocyanine complexes encapsulated in zeolite-Y
S. Seelan, D. Srinivas, M.S. Agashe, N.E. Jacob and S. Sivasanker
349
14-P-13 - Investigations on isomorphous substitution and catalytically active centres in MeAPO-31 (Me = Mn, Co, Zn, Ti)
N. Novak Tusar, A. Ristic, A. Ghanbari-Siahkali, J. Dwyer, G. Mali, I. Arcon and V. Kaucic
349
14-P-14 - A comparative study of Ti 4+ sites in titanium silicalite (TS-1) synthetized by different methods
N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, M.V. CagnolL S.G. Marchetti and A.A. Yeramian
349
14-P-15 - Behaviour of Fe(III) ions in Y zeolites in the presence of Cu(II) and Ag(I) ions: an ESR study
A.L. Kustov, E.E. Knyazeva, E.A. Zhilinskaya, A. Aboukais and B. V. Romanovsky
350
14-P-16 - FT-Raman spectroscopic studies of host-guest interactions in zeolites
Y. Huang, J.H. Leech and R.R. Poissant
350
xlvi 14-P-17 - High-temperature MAS NMR investigation of the mobility of cations and guest compounds in zeolites X and Y M. Hunger, A. Buchholz and U Schenk
350
14-P-18 - Generation of long-lived electron-hole pairs through sorption of biphenyl into acidic ZSM-5 zeolites I. Gener, A. Moissette, H. Vezin, J. Patarin and C. Br~mard
351
14-P-19 - Defects study in microporous materials by HRSEM, HRTEM and diffraction techniques G. Gonzalez, Z Lopez and R. Reichelt
351
14-P-20 - The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites and their photocatalytic reactivity S. Higashimoto, M. Matsuoka, M. Che and M. Anpo
351
14-P-21 -Characterization of aluminium and iron sites in MCM-22 J. (;ejka, J. D~dedek, J. Kotrla, M. Tudor, N. Zilkovct and S. Ernst
352
14-P-22 - Valency and coordination states of iron in FeAPO-11. An in-situ M6ssbauer study K. L6z6r, N. Zilkov6 and J. Cejka
352
14-P-23 - C o m p a r a t i v e properties of modified HEMT and HY zeolites from the FTIR study of CO adsorption: effect of the dealumination and amorphous debris on the Br6nsted acidity O. Cairon and T. Chevreau
352
14-P-24 - Raman spectroscopic study of 2,2'-bip;cridine sorbed into ZSM5 A. Moissette, C. Br~mard, 1. Gener and N. Louchart
353
14-P-25 - Fractals of silica aggregates Z. Li, D. Wu, Y.-H. Sun, J. Wang, Yi Liu and B. Dong
353
14-P-26 - Structure of Mo species incorporated into SBA-1 and SBA-3 studied by XAFS and UV-VIS spectroscopies H. Yoshitake, S.H. Lim, S. Che and T. Tatsumi
353
14-P-27 - Quantification of electric-field gradients in the supercage of Y zeolites by comparing the chemical shifts of 131Xe (I = 3/2) and 129Xe (I = 1/2) Y. Millot, P.P. Man, M.-A. Springuel-Huet and J. Fraissard
354
14-P-28 - Iron species present in Fe/ZSM-5 catalysts prepared by ion exchange in aqueous medium or in the solid state M.S. Batista, M.A.M. Torres, E. Baggio-Saitovich and E.A. Urquieta-Gonz6lez
354
xlvii
14-P-29 - Laser ablation mass spectrometry : a technique for observing zeolite occluded molecules
S. Jeong, K.J. Fisher, G.D. Willett and R.F. Howe
354
14-P-30 - Characterisation of TS-1 active sites by adsorption of organic probes C. Flego, A. Carati and M.G. Clerici
355
14-P-31 - NIR FT-Raman spectroscopy on molecular sieves E. LOftier and M. Bergmann
355
14-P-32 - Characterization of Zn and Fe substituted mordenite by XAFS M. Dong, J.-G. Wang and Y.-H. Sun
355
14-P-33 - Identification of vanadium species in VAPO and VAPSO aluminophosphate by UV resonance raman spectroscopy
Jia. Yu, Z. Liu, Q. )(in and C. Li
356
14-P-34 - On the interaction of H20 with TS-1: a spectroscopic and ab-initio study
A. Damin, G. Ricchiardi, S. Bordiga, F. Bonino, A. Zecchina, F. Ricci, G. Span6, F. Villain, and C. Lamberti
356
14-P-35 - Spectroscopic study of the nature of vanadyl groups: influence of the support (SiO z and All3 and SiB zeolites).
S. Dzwigaj, M. Matsuoka, M. Anpo and M. Che
356
14-P-36 - Characterization ofNi, Pt zeolite catalysts by TEM and EDX M.H. Jord6o and D. Cardoso
357
14-P-37 - NMR and ESR investigations of alkali metal particles in NaY zeolite F. Rachdi and L.C. de M~norvat
357
14-P-38 - Topochemical changes in large MFI-type crystals upon thermal treatment in oxidizing and non-oxidizing atmosphere
O. Pachtov6, B. Bernaue, J.-A. Dalmon, S. Miachon, I. Jirka, A. Zik6nov6 and M. Kodi(ik
357
14-P-39 - Structure of Fe(III) sites in iron substituted aluminophosphates: a computational and X-ray spectroscopic investigation
C. Zenonos, A. Beale, G. Sankar, D.W. Lewis, J.M. Thomas and C.R.A. Catlow
358
14-P-40 - Possible formation of Cu+2(CO)2(H20)n complexes in a ZSM-5 zeolit.e prepared by direct synthesis: evidence for the occurrence of Cu+-Cu + pairs?
F. Geobaldo, B. Onida, M. Rocchia, S. Valange, Z Gabelica and E. Garrone
358
xlviii 15 - Modelling and Theoretical Studies A 15-0-01 - Proton jumps in dehydrated acidic zeolite catalysts. Rate predictions based on ab-initio calculations
M. Sierka and J. Sauer
148
15-0-02 - Ab-initio simulation of dynamical processes in zeolites L. Benco, T. Demuth, J.Hafner, F. Hutschka and 14. Toulhoat
148
15-0-03 - A theoretical study of the methylation of toluene by methanol over acid mordenite
A. Vos, X. Rozanska, R. Schoonheydt, R. van Santen, F. Hutschka and J. Hafner
149
15-0-04 - Coverage effects on adsorption of water in faujasite: An ab-initio cluster and embedded cluster study
J. Limtrakul, S. Nokbin, P. Chuichay, P. Khongpracha, S. Jungsuttiwong and T.N. Truong
149
15-0-05 - The Beckmann rearrangement catalyzed by silicalite: a spectroscopic and computational study
G.A. Fois, G. Ricchiardi, S. Bordiga, C. Busco, L. Dalloro, G. Span6 and A. Zecchina
149
15-P-06 - A reactivity index study to choose the best template for zeolite synthesis
A. Chatterjee and T. lwasaki
256
15-P-07 - Effects of ion-exchanged alkali metal cations on the photolysis of alkyl ketones included within ZSM-5 zeolite cavities: A study of ab-initio molecular orbital calculations
H. Yamashita, S. Takada, M. Nishimura, H. Bessho and M. Anpo
256
15-P-08 - Encapsulated guest atoms within the basic beta cage of sodalitic zeolite. A theoretical ab-initio study
N. U. Zhanpeisov and M. Anpo
256
15-P-09 - n-Hexane aromatization over Pt-alkaline zeolites: ab-initio calculations on the influence of the exchanged cations and zeolite type (L, 13 and Y) on electronic properties of Pt
S.B. Waghmode, P. Bharathi, R. Vetrivel and S. Sivasanker
257
15-P-10 - A theoretical study of adsorption of carbon monoxide on Ag-ZSM-5 zeolite
S. Jungsuttiwong, P. Khongpracha, T.N. Truong and J. Limtrakul
257
15-P-11 - A theoretical/spectroscopic study of the coordination of transition metal ions in zeolites
A. Delabie, M.H. Groothaert, R.A. Schoonheydt and K. Pierloot
257
xlix 15-P-12 - Ab-initio study of the adsorption and reactions of hydrocarbons in mordenite T. Demuth, L. Benco, J. Hafner, H. Toulhoat and F. Hutschka
258
15-P- 13 - Properties of C u 2+ and Cu + cations in MFI framework: DFT and IR studies E. Broclawik, J. Datka, B. Gil and P. Kozyra
258
15-P-14 - Nonempirical (ab-initio) and semiempirical calculations of the elementary fragments of zeolites. Permeability of rings zeolite fragments A.V. Gabdrakipov, L.D. Volkova, N.A. Zakarina and V.Z Gabdrakipov
258
15-P-15 - Modelling light alkane transformation over HZSM-5 zeolite X. Wang, F. Lemos and F.R. Ribeiro
259
15-P-16 - Activity-acidity relationship in Y zeolite: an experimental and quantumchemical study X. Wang, M.A.N.D.A. Lemos, F. Lemos, C. Costa and F.R. Ribeiro
259
15-P-17 - DFT study of structure changes in hydrated A1PO4-n: The case of A1PO4-34 G. Poulet, A. Tuel and P. Sautet
259
15-P-18 - A mechanistic exploration of alkene epoxidation mediated by H202 within porous titanosilicate catalysts C.M. Barker, N. Kaltsoyannis and C.R.A. Catlow
260
15-P-19 - Transition-state shape-selectivity insights from a Fukui function overlap method L.A. Clark and R. Q. Snurr
260
15-P-20 - A DFT study of the isomerization reactions of aromatics catalyzed by acidic zeolites X. Rozanska, R.A. van Santen, F. Hutschka and J. Hafner
260
15-P-21 - Ab-initio investigation of non-framework aluminum species in zeolites D. Lopes Bhering, C.J.A. Mota and A. Ramirez-Solis
261
15-P-22 - A DFT study of the cracking reaction of thiophene activated by zeotype catalysts: role of the basic Lewis site X. Rozanska, R.A. van Santen and F. Hutschka
261
15-P-23 - Modelling transition metal cations in zeolites: how do they interact with the framework? D. Berthomieu, A. Goursot, J-M. Ducdr~, G. Delahay, B. Coq and A. Martinez
261
15-P-24 - Theoretical prediction of IR spectra of guest molecules in zeolites: the stretching frequency of CO adsorbed at various cationic sites in ZSM-5 T.A. Wesolowski, A. Goursot and J. Weber
262
15-P-25 - Development of a tight-binding treatment for zeolites M. Elstner, A. Goursot, Z. Hajnal, T. Heine and J. Weber
262
15-P- 26 - 1-D growth of selenium wires in silicalite-1 zeolite C. Bichara and R.J.-M. Pellenq
262
15-P-27 - Cumulative coordinates for approximations of atomic multipole moments in cationic forms of aluminosilicates A. V. Larin and D.P. Vercauteren
263
15-P-28 - Computer simulations of water in zeolites C. Bussaia, R. Haberlandt, S. Hannongbuai and S. Jost
263
16 - Modelling and Theoretical Studies B 16-0-01 Simulating shape selectivity in alkane hydroconversion by zeolites M. Schenk, T.L.M. Maesen and B. Smit
155
16-O-02 - Molecular dynamics of the faujasite (111) surface B. Slater and C.R.A. Catlow
155
16-0-03 - Adsorption of xylene isomers and water in faujasites. A molecular simulation study S. Buttefey, A. Boutin and A.H. Fuchs
155
16-0-04 - Reaction dynamics in acidic zeolites: room temperature tunneling effects J. T. Fermann and S.M. Auerbach
156
16-0-05 - Molecular modeling of multicomponent diffusion in zeolites and zeolite membranes M.J. Sanborn, A. Gupta, L.A. Clark and R.Q. Snurr
156
16-P-06 - Location of triethylmethylammonium ions in MFI by combining molecular modeling and X-ray diffraction R. Millini
264
16-P-07 - A hypothetical zeolite structure MCR16: topological design and template choice B. Li, P. Sun, Q. Jin and D. Ding
264
16-P-08 - Computational analysis of the shape-selective isopropylation of biphenyl over large pore zeolites
J. Joffre, D. Mravee and P. Moreau
264
16-P-09 - De novo simulation and spectroscopic study of iron speciation in ZSM-5 and CIT-5
P.-PH.J.M. Knops-Gerrits and W.A. Goddard III
265
16-P-10 - Exact statistical mechanical treatment of a lattice model of hydrocarbon adsorption on zeolites
G. Manos, L.J. Dunne, Z Du and M.F. Chaplin
265
16-P-11 - Computational studies of the structure of Na- and H-Mordenite
A.E. Gray, A. 0 'Brien and D. W. Lewis
265
16-P-12 - Monte Carlo simulation of isobutane in silicalite
D. Paschek and R. Krishna
266
16-P- 13 - Characterisation of hypothetical zeolite frameworks
M.D. Foster, R.G. Bell and J. Klinowski
266
16-P-14 - Cation mobility and the sorption of chloroform in zeolite NaY: a molecular dynamics study
N.A. Ramsahye and R.G. Bell
266
16-P- 15 - Computational studies of the calcination of fluorinated gallophosphates: exploration of their template-free calcined forms
S. Girard, J.D. Gale, C. Mellot-Draznieks and G. Fdrey
267
16-P-16 - Molecular simulation studies on the effectiveness of template type on TS- 1 crystal morphology
tl. Zhou, H. He and Z Jing
267
16-P-17 - A molecular dynamic approach on the selective conformational change of ethylene glycol in sodalite cage
M. Sato
267
16-P-18 - The mutual influence of dynamic processes acting in different time scales
S. Fritzsche, R. Haberlandt, A. Schfiring and M. Wolfsberg
268
16-P-19 - Lattice-dynamical calculations for zeolites of natrolite group
S. V. Goryainov and M.B. Smirnov
268
16-P-20 - Kinetic modelling of the dynamic interaction between NO and N20 over Cu-ZSM5
R. Pirone, P. Ciambelli, A. Di Benedetto, B. Palella and G. Russo
268
lii
17- Principles of Adsorption 17-0-01 - Liquid-solid and solid-solid phase transitions of oxygen in a single cylindrical pore
K. Morishige and Y. Ogisu
137
17-0-02 - Structural study of benzene, tetrachloroethene and trichloroethene sorbed phases in silicalite-1
N. Floquet, J.P Coulomb, G. Weber, O. Bertrand and J.P Bellat
137
17-0-03 - Molecular ordering of the adsorbed phase within the microporous model aluminophosphate A1PO4-11 at cryogenic temperatures
N. Dufau, N. Floquet, J-P. Coulomb, P.L. Llewellyn and J. Rouquerol
137
17-0-04 - - Adsorption properties of a supercritical fluid on mesoporous molecular sieves under high pressure
Ya. Goto, N. Setoyama, Y. Fukushima, T. Okubo, Yu. Goto, Y. lmada, Y. Kubota and Y. Sugi
138
17-P-05 - Confinement in model host materials: experimental study of quasi-(1 d) systems.
J.P. Coulomb, N. Floquet, C. Martin, Y. Grillet and J. Patarin
222
17-P-06 - Studies on desorption behavior of organics on siliceous ferrierite B. Qian, Y. Zeng and Y.-C. Long
222
17-P-07 - Investigation of hydrocarbon adsorption on large and extra-large pore zeolites
C. Y. Chen and S.I. Zones
222
17-P-08 - Different chemisorption methods applied to zeolite supported Pt-catalysts
J.C. Groen, J. P~rez-Ramirez and L.A.A. Peffer
223
17-P-09 - Structure vs. adsorption properties of 5A zeolites H. Paoli, T. Bataille, B. Rebours, A. M~thivier and H. Jobic
223
17-P-10 - Hydrogen adsorption in lithium exchanged Na A zeolites S. Kayiran, F. Darkrim and A. Gicquel
223
17-P- 11 - Macroscopic and microscopic investigations of the interaction of a chloroalkene on a MFI zeolite
V. Francois, S. Maure, F. Bouvier, G. Weber, O. Bertrand, J.P. Bellat and C. Paulin
224
17-P-12 - Sorption and pore condensation behavior of pure fluids in mesoporous MCM-48 silica, MCM-41 silica and controlled pore glass
M. Thommes, R. KOhn and M. FrOba
224
liii
17-P-13 - Pore size analysis with H20 adsorption measurement of organically modified MCM-41 type materials
N. Igarashi, K. Nakai, K. Hashimoto and T. Tatsumi
224
17-P-14 - Adsorption of carbon dioxide by X zeolites exchanged with Z n 2+ and Cu2+: isosteric heat and adsorption isotherms
A. Khelifa, Z. Derriche and A. Bengueddach
225
17-P-15 - A combination of high resolution manometry, gravimetry and microcalorimetry to study the co-adsorption of Ar/N2 mixtures on 5A and 13X zeolites
S. Moret, F. Rouquerol, J. Rouquerol and P.L. Llewellyn
225
17-P-16 - Gas adsorption microcalorimetry on zeolites under supercritical conditions up to 15 bars
T. Poyet, F. Rouquerol, J. Rouquerol and P.L. Llewellyn
225
18- Adsorption and Separation Process 18-0-01 - An experimental adsorbent screening study for CO2 removal from flue gas
P.J.E. Harlick, H. Halsall-Whitney and F. Handan Tezel
143
18-0-02 - Amino acids in BEA type channels
C. Buttersack and A. Perlberg
143
18-O-03 - Kinetic separation of binary mixtures of carbon dioxide and C2 hydrocarbons on modified LTA-type zeolites
C.J. Guo, D. Shen and M. Btilow
144
18-0-04 - A novel adsorbent for the separation of propane/propene mixtures
W. Zhu, F. Kapteijn and J. A. Moulijn
144
18-0-05 - Iodide removal using zeolite-based reactive adsorption
S. Kulprathipanja and B. Spehlmann
144
18-P-06 - Evaluation of mesoporous silicas as stationary phases for high performance liquid chromatography (HPLC)
L. Sierra, B. Lopez, A. Ramirez and J.-L. Guth
226
18-P-07 - Adsorption of N-nitrosamines by zeolites in solutions
Ying Wang, J.H. Zhu, D. Yan, W. Y. Huang and L.L. Ma
226
18-P-08 -An adsorption-desorption process for separation of C8 aromatics
G.-Q. Guo and Y.-C. Long
226
liv 18-P-09 - Preparation of Na-A zeolite capillary columns by in-situ synthesis
D. Kou, Z. Li, J. Wu, Ming Liu and S. Xiang
227
18-P-10 - Adsorption of C02, S02 and NH3 on zeolitic materials synthesized from fly ash
S. Herndndez, R. Juan, X. Querol, N. Moreno, P. Ferrer and J.M. Andrds
227
18-P-11 - Dibenzothiophene adsorption over zeolites with faujasite structure
J.L. Sotelo, M.A. Uguina, M.D. Romero, J.M. G6mez, V.I. Agueda and M.A. Ortiz
227
18-P-12 - Pressure swing adsorption of ethyl acetate on silica MCM-41
S. Namba, D. Yomoda, J. Aoyagi, K. Minagawa, T. Kugita and J. Izumi
228
18-P-13 - P occlusion in LTA: an approach for enhancing N2 adsorption properties
L. Johnson and M. Miller
228
18-P-14 - Sulfur guard bed material from local bentonite deposits
S. Mikhail and T. Zaki
228
18-P- 15 - Simulation for removal of binary solvent vapor by adsorption onto high silica zeolite.
K. Chihara, T. Saito, H. Suzuki, H. Yamaguchi and Y. Takeuchi
229
1 9 - Diffusion: Fundamental Approach 19-0-02 - Studies of adsorption, diffusion and molecular simulation of cyclic hydrocarbons in MFI zeolites
L. Song, Z L. Sun and L. V. C Rees
153
19-0-03 - The effect of silanisation on the intracrystalline diffusivity of ZSM-5
W.L. Duncan and K. P. MOller
154
19-0-04 - Interference microscopy as a tool of choice for investigating the role of crystal morphology in diffusion studies
O. Geier, S. Vasenkov, E. Lehmann, J. Kgirger, R.A. Rakoczy and J. Weitkamp
154
19-0-05 - Estimation of the interphase thickness and permeability in polymerzeolite mixed matrix membranes
A. Erdem-~enatalar, M. Tather and ~.B. Tantekin-Ersolmaz
154
19-P-06 - Modeling of sulfur dioxide breakthrough curves from ternary wet mixtures on MOR type zeolite
M. Mello, M. EiO, S. Ho&var and U. Lavrendid-Stangar
269
lv 19-P-07 - The diffusion and sorption dynamics of acetylene in zeolites Gy. Onyesty6k, J. Valyonand and L. K C. Rees
269
19-P-08 -Transient uptake measurements using an oscillating microbalance: effect of acid leaching on the diffusivity of n-hexane in Pt/H-Mordenite S. van Donk, A. Broersma, O.L.J. Gijzeman, J.H. Bitter and K.P. de Jong
269
19-P-09 - Use of 129XeNMR spectroscopy to study gaseous hydrocarbon diffusion in a fixed bed of HZSM-5 zeolite M.-A. Springuel-Huet, P N'Gokoli-Kekele, C. Mignot, J.-L. Bonardet and J. Fraissard
270
19-P-10 - Adsorption and diffusion of alkanes and their mixtures in silicalite studied with positron emission profiling technique A. O. Koriabkina, D. Schuring, A.M. de Jong and R.A. van Santen
270
2 0 - Zeolite Membranes and Films 20-0-01 - Polyamines as strong covalent linkers for the assembly of mono and double layers of zeolite crystals on glass K. Ha, Y.S. Chun, A. Kulak, Y.S. Park, Y. -J. Lee and K.B. Yoon
161
20-0-02 - The use of seeds in the synthesis of mono-and bi-layered zeolite membranes L. Gora, G. Clet, J.C. Jansen and Th. Maschmeyer
162
20-0-03 - Growth of oriented mordenite membranes on porous (x-AI203 supports G. Li, X. Lin, E. Kikuchi and M. Matsukata
162
20-0-04 - Depth-sensitive structural study of silicalite-1 films with grazing incidence X-ray diffraction S. Mintova, T.H. Metzger and T. Bein
162
20-0-05 - Regeneration of supercritical carbon dioxide by alumina supported MFI zeolite and mesoporous silica membranes K.J. Chao, C.H. Kao, Y.W. Chiu, X.R. Lin and C.S. Tan
163
20-P-06 - Dehydrogenation of ethylbenzene to styrene using ZSM-5 type zeolite membranes as reactors X.-F. Zhang, Y.-S. Li, J.-Q. Wang, H.-O. Liu and C.-H. Liu
291
20-P-07 - Preparation of high-permeance ZSM-5 tubular membranes by varyingtemperature synthesis Y.-S. Li, Xio. Zhang, J.-G. Wang and S. Guo
291
lvi
20-P-08 - Synthesis of FAU type films on steel supports using a seeding method
Z Wang, J. Hedlund and J. Sterte
291
20-P-09 - Structured zeolite ZSM-5 coatings on ceramic packing materials
O. Ohrman, U Nordgren, J. Hedlund, D. Creaser and J. Sterte
292
20-P-10 - Effects of synthesis parameters on intra-pore zeolite formation in zeolite A membranes
M. Lassinantti, J. Hedlund and J. Sterte
292
20-P-11 Pure-silica zeolite low-k dielectric thin films by spin-on process
Zhen. Wang, H. Wang, A. Mitra, L. Huang and Yu. Yan
292
20-P-12 - Preparation of silicalite-1 and beta zeolite/ceramic composite membranes and removal of trace phenol and benzene from water through them 293
Xiansen Li and S. Xiang 20-P-13 - Factors affecting film thickness in the preparation of supported ZSM-5 zeolite
E.I. Basaldella, A. Kikot, J.E Bengoa andJ. C. Tara
293
20-P-14 - Growing zeolite films onto gold surfaces
E I. Basaldella, A. Kikot, J.O. Zerbino and J.C. Tara
293
20-P- 15 - Diffusivities of zeolite coatings
M. Tather, ~.B. Tantekin-Ersolmaz andA. Erdem-~enatalar
294
20-P-16 - Crystal growth mechanism of LTA and FAU and densification process of zeolite film by seed growth
I. Kumakiri, Y. Sasaki, W. Shimidzu, T. Yamagushi. and S.-I. Nakao
294
20-P-17 - In-situ synthesis of ZSM-5 on aluminum surfaces F. Scheffler and W. Schwieger
294
20-P- 18 - Conceptual process design of an all zeolite membrane reactor for the hydroisomerization of CflC6
E.E. McLeary, R.D. Sanderson, C. Luteijn, E.J.W. Buijsse, L. Gora, Th. Maschmeyer and J. C. Jansen
21 - N a n o c o m p o s i t e
Fundamentals
295
and Applications
21-O-02 - Methods of synthesis for the encapsulation of dye molecules in molecular sieves
M. Wark, M. Ganschow, Y. Rohlfing, G. Schulz-Ekloff and D. Wohrle
160
lvii 21-O-03 -MCM-41 silica monoliths and diluted magnetic semiconductors: a promising union for fabricating nanosized quantum wires
F. Brieler, M. Brehm, L. Chen, P.J. Klar, W. Heimbrodt and M. FrOba
160
21-O-04 - Potential microlasers based on AIPO4-5/DCM composites
O. Weifl, F. Schuth, L. Benmohammadi and F. Laeri
161
21-O-05 - Light-emitting BN, Si, and SiC nanoparticles encapsulated in molecular sieves
Xiaotian Li, C. Shao, F. Gao, S. Qiu, F.-S. Xiao and O. Terasaki
161
2 l-P-06 - Fabrication of hollow fibers and spheres composed of zeolites by layerby-layer adsorption method
E Tang, Y.-J. Wang, X.-D. Wang, W.-L. Yang and Z. Gao
296
2 l-P-07 - The zeolitisation of diatoms to create hierarchical pore structures
S.M. Holmes, R.J. Plaisted, P. Crow, P. Foran, C.S. Cundy and M. W Anderson
296
2 l-P-08 - Generating the narrowest single-walled carbon nanotubes in the channels of A1PO4-5 single crystals
G.D. Li, Z.K. Tang, N. Wang, K.H. Wong and J.S. Chen 21-P-09
-
296
Zeolite- an effective nucleating agent of NazHPO4" 12H20
J. Dong, X. Jing and Yu. Zhang
297
2 l-P-10 - Synthesis and characterization of SnO2 nano particles in zeolite hosts
Yi. Zhang, Xu. Wang and Xi. Wang.
297
2 l-P-11 - Encapsulation of Mn(bipy)2 into the zeolite Y prepared via different routes
B. Fan, W Cheng and R. Li
297
2 l-P-12 - Preparation of zeolite Beta/polystyrene beads and the corresponding hollow spheres
V. Valtchev and S. Sferdjella
298
2 l-P-13 - Synthesis, characterization and catalysis of manganese(II) complexes encapsulated in NaX and NaY zeolites
J.M. Silva, R. Ferreira, C. Freire, B. de Castro and J. L. Figueiredo
298
2 l-P-14 - Guest-host interactions in systems containing liquid crystals confined to molecular sieves
S. Frunza, L. Frunza, A. SchOnhals, H.-L. Zubowa, H. Kosslick and R. Fricke
298
2 l-P-15 - Zeolite Beta ordered macroporous structures with improved mechanical strength and controlled mesoporosity
V. Valtchev, S. Sferdjella and H. Kessler
299
lviii 2 l-P- 16 - Synthesis of zeolites with organic lattice
K. Yamamoto, Y. Takahashi and T. Tatsumi
299
2 l-P-17 - Crystallization mechanism of A1MePO-I3
Y. Qi, G. Wang and Z. Liu
299
2 l-P-18 - Crystal structure and magnetic properties of rubidium clusters in zeolite LTA
T. Ikeda and T. Kodaira
22 - Advanced
300
Materials
22-0-01 - The effect of the location of framework negative charge on the ordering of templates in zeolite IFR
R.E. Morris and L.A. Villaescusa
168
22-0-02 - A new family of microporous vanadium phosphates and related compounds with organic coordination
S. Feng, Z. ShL L. Zhang, H. Zhao, D. Zhang and Z Dai
168
22-0-03 - Catalytic properties of novel nickel(II) phosphate with nanoporous structure
J.-S. Chang, D.S. Kim, S.-E. Park, P.M. Forster, A.K. Cheetham and G. Ferey
169
22-0-04 - Characterization of corrosion-resistant zeolite coatings on A1 alloys
H. Wang, Zhen. Wang, X. Cheng, A. Mitra, L. Huang and Y. Yan
169
22-0-05 - Template synthesis and catalysis of bimetallic platinum-rhodium and palladium nanowires in mesoporous materials
A. Fukuoka, Y. Sakamoto, S. Inagaki, iV. Sugimoto, Y. Fukushima and M. Ichikawa
169
22-P-06 - Tailored generation of titanium oxide species within porous Si-MCM-41
P. Prochnow, G. Schulz-Ekloff M. Wark, J.K. Thomas, A. Zukal and J. Rathousky
359
22-P-07 - Optical switching with photochromic dye molecules encapsulated in the pores of molecular sieves by in-situ synthesis
C. Schomburg, D. WOhrle, G. Schulz-Ekloff and M. Wark
359
22-P-08 - Formation of carbon nanotubes on various molecular sieves supported metal oxides
A. M Zhang, Q H. Xu, J.J. Zhao and J.M. Cao
359
lix 22-P-09- Encapsulation of Tb[(C1BOEP)4P](acac) in Si-MCM-41 by the method of ship-in-bottle and its luminescent properties at 77 K
Q Xu, Z. Zhao, L. LL G. Liu, 11. Ding, J. Yu and R. Xu
360
22-P-10 - A new adsorbent with magnetic properties based on natural clinoptilolite
V. Pode, V. Georgescu, V. Dalea, R. Pode and E. Popovici
360
22-P-11 - Preparation of microcalorimetric gas sensors with CoAPO-5
S. Mintova, J. Visser and T. Bein
360
22-P-12 - Study of cation-exchange properties of an organozeolite
V.A. Nikashina, E.M. Kats, 1. V. Komarova, N.K. Galkina and K.1. Sheptovetskaja
361
22-P-13 - Advanced electrode materials based on mesoporous aluminumstabilized anatase
A. Attia, S.H. Elder, R. Jir6sek, L. Kavan, P. Krtil, J. Rathousk~ and A. Zukal
361
22-P-14 - Dye-zeolite assemblies for optical sensing applications
J.L. Meinershagen and T. Bein
361
22-P-15 - A new sorbent based on clinoptilolite-containing tuff modified by polyethylene
1.N. Meshkova, V.A. Nikashina, T.M. Ushakova, V.G. Grinev, N. Yu. Kovaleva, A.A. Zaborskii, T.A. Ladygina and L.A. Novokshonova
362
22-P-16 - Molecular sieves from pillaring of some romanian bentonite
E. Popovici, 1. Bedelean, D. Pop, G. Singurel, D. Macocinschi and H. Bedelean
362
22-P-17 - Electronic states and arrangements of AgI and CuI clusters incorporated into zeolite LTA
T. Kodaira and T. Ikeda
362
22-P-18 - PbI2 nanoclusters in zeolite LTL: host-guest chemistry and optical properties
G. Telbiz, O. Shvets, V. Vozny and M. Brodyn
363
22-P-19 - Application of the molecular sieves as matrices for the pigments
S. Kowalak, A. Jankowska, N. Pietrzak and M. Str6zyk
363
22-P-20 - Laser dye doped mesoporous silica fibers: host-guest interaction and fluorescence properties
363
G. Telbiz, O. Shvets, S. Boron, V. Vozny, M. Brodyn and G. Stucky 22-P-21 - Spectroscopic properties of dye-loaded mesoporous silicas of the structural type MCM-41
B. Onida, B. Bonelli, M. Lucco-Borlera, L. Flora, C. Otero Aredn and E. Garrone
364
lx 23 - M i c r o - a n d M e s o p o r o u s
M a t e r i a l s in F i n e C h e m i s t r y
23-0-02 - Pd-zeolites as catalysts for the Heck reaction: a screening of reaction parameters affecting catalyst heterogeneity M. Dams, D.E. De Vos, L. Drij'koningen and P.A. Jacobs
138
23-0-03 - Beckmann rearrangement of cyclohexanone oxime over mesoporous MCM-41 and MCM-48 type materials R. Glaser, 11. Kath and J. Weitkamp
139
23-0-04 - Knoevenagel condensation between ethylcyanoacetate and benzaldehyde over base catalysts immobilized on mesoporous materials Y. Choi, K.-S. Kim, J.-H. Kim and G. Seo
139
23-0-05 - One-step synthesis of MIBK from acetone over Pt/X catalysts L. V. Mattos, F.B. Noronha andJ.L.F. Monteiro
139
2 3 - P - 0 6 - Selective hydroxyethylation of furfuryl alcohol with aqueous acetaldehyde in the presence of H-form zeolites A. Finiels, W. Balmer and C. Moreau
230
23-P-07 - Selective synthesis of monooctylamines by ammonia alkylation with octanol using NaY, ZSM-5, SAPO-5, SAPO-1 l, SAPO-31, SAPO-34 S. Amokrane, R. Rebai, S. Lebaili, D. Nibou and G. Marcon
230
23-P-08 - Conversion of monoethanolamine in other organic nitrogen compounds on H-mordenite and H-clinoptilolite G. Torosyan, S. Sargsyan and A. Grigoryan
230
23-P-09 - The influence of ammonia adsorption on Y Zeolite and natural clinoptilolite activity in ethanol transformation L. Akhalbedashvili, A. Mskhiladze and Sh. Sidamonidze
231
23-P-10 - Enantioselective synthesis and separation of terminal epoxides and diols using a catalytic membrane system containing chiral Co(III) salen S.-D. Choi and G.-J. Kim
231
23-P-11 - Asymmetric trimethylsilylcyanation of benzaldehyde catalyzed by chiral Yi(IV) salen complexes immobilized on MCM-41 J.-H. Kim and G.-J. Kim
231
23-P-12 - Mechanistic study of aniline methylation over acidic and basic zeolites Y 1.1. lvanova, E.B. Pomakhina, A.1. Rebrov, Yu.G. Kolyagin, M. Hunger and J. Weitkamp
232
23-P-13 - Heterogeneous base catalysis" characterization of zeolites and mixed oxides using nitromethane as a NMR probe molecule and activity in the Michael condensation of nitromethane and cyclohex-2-en-l-one E. Lima, L.-C. de Mdnorval, M. Laspdras, J.-F. Eckhard, D. Tichit, P. Graffin and F. Fajula
232
lxi 23-P-14 - Synthesis of ot-pinene derivatives using redox-mesoporous molecular sieves
Y.-W. Suh, T.-M. Son, N.-K. Kim, W.-S. Ahn and H.-K. Rhee
232
23-P-15 - Ring opening reactions of methyloxirane over DZSM-5 and DA1MCM-41 molecular sieves - A mechanistic study
A. Fdsi, I. Pdlink6, ,4. GOmOry and I. Kiricsi
233
23-P-16 - Hydrodechlorination of 1,2,4-trichlorobenzene on Ni/A1-MCM-41 catalysts
Y. Cesteros, P. Salagre, F. Medina, J.E. Sueiras and G.L. Haller 23-P-17
-
233
Adsorption of cytochrome c onto ordered mesoporous silicates
J. Deere, E. Magner, J.G. Wall and B.K. Hodnett
233
23-P-18 - Vapor phase Beckmann rearrangement of cyclohexanone oxime over tantalum pillared magadiite
S.J. Kim, M.H. Kim, Y. Ko, G. Seo and Y.S. Uh
234
23-P-19 - Hydration of a-pinene over heteropolyacids encaged.in USY zeolites
J. Vital, A.M. Ramos, I.F. Silva, J.E. Castanheiro, M.N. Blanco, C. Caceres, P. Vasquez, L. Pizzio and H. Thomas
234
23-P-20 - Selective adsorption of trans unsaturated fatty acid compounds in MFI type zeolites
S. Paulussen, M. Goddeeris and P.A. Jacobs
234
23-P-21 - Novel delaminated zeolites are more active acid catalysts than conventional zeolites and mesoporous AI/MCM-41 for the synthesis of fine chemicals
M.J. Climent, A. Corma, V. Fornds, H. Garcia, S. Iborra, J. Miralles and I. Rodriguez
235
23-P-22 - The design of zeolites catalysts for the synthesis of orange blossom and apple fragrances
M.J. Climent, A. Corma and A. Velty
235
23-P-23 - Catalytic in-situ infrared spectroscopic study of n-butyraldehyde aldol condensation
U. Rymsa, M. Hunger and J. Weitkamp
235
23-P-24- Oxyhalogenation of aromatic compounds in presence of KC1 or KBr and H202 over zeolites.
N. Narender, P. Srinivasu, S.J. Kulkarni and K. V. Raghava~
236
lxii 23-P-25 - Synthesis and characterization of mesoporous Pt-MCM-41 and its application in enantioselective hydrogenation of 1-phenyl-1,2-propanedione
E. Toukoniitty, B. Sevcikovdt, N. Kumar, P. Mdiki-Arvela, T. Salmi, J. Vdiyrynen, T. Ollonqvist, E. Laine, P.J. Kooyman and D. Yu. Murzin
236
23-P-26 - Isomerization of p-eugenol on palladium-containing zeolites
Ts.M. Ramishvili, M.K. Charkviani and L.D. Kashia
236
23-P-27 - The use of MCM-22 as catalyst for the Beckmann-rearrangement of cyclohexanone oxime to e-caprolactam
G. Dahlhoff U. Barsnick, W. Eickelberg and W.F. HOlderich
237
23-P-28 - Nickel supported on zirconium doped mesoporous silica as catalysts for the gas phase hydrogenation of acetonitrile
P. Braos-Garcia, L. Diaz, P. Maireles-Torres, E. Rodriguez-Castell6n and A. Jim6nez-L6pez
237
23-P-29 - Synthesis of fine chemicals intermediates over basic zeolites
C.O. Veloso, A.C. Pinto, E.N. Santos and J.L.F. Monteiro
237
23-P-30 - Selective chlorination of diphenylmethane over zeolite K-L 238
A.P. Singh and S.M. Kale 23-P-31 - Butylation of phenol on medium pore A1PO4 -11, -31 and -41 structures: effect of silicon incorporation
C. V. Satyanarayana, U. Sridevi and B.S. Rao
238
23-P-32 - The catalytic synthesis of the glycidol from the glycerol carbonate in presence of zeolite A 238
J. W. Yoo and Z. Mouloungui 23-P-33 - Transfer hydrogenation of unsaturated ketones catalyzed by Al-isopropoxide dispersed on MCM-41
J. Wahlen, D.E. De Vos, M. De bruyn, PJ. Grobet and PA. Jacobs
2 4 - N e w R o u t e s to H y d r o c a r b o n
239
Activation
24-0-01 - Dehydroisomerization of n-butane to isobutene over Pd modified silicoaluminophosphate molecular sieves
Y. Wei, G. Wang, Z. Liu, C. Sun and L. Xu
145
24-0-02 - Conversion of methane over Ag-Y in the presence of ethene
T. Baba, H. Sawada, Y. Abe and Y. Ono
145
24-0-03 - Peculiarities in the hydroconversion of n-hexadecane over bifunctional catalysts
L. Perrotin, A. Finiels, F. Fajula and T. Cholley
145
lxiii 24-0-04 - HI3 catalyzed heterogeneous aziridination of olefins
B. Chanda, R. Vyas, A. V. Bedekar, B.B. Kasture and V.N. Joshi
146
24-0-05 - MCM-41 as support for metallocene catalysts - ethylene polymerization
C.A. Henriques, M.F.V. Marques, S. Valange, Z Gabelica and J.L.F. Monteiro
146
24-P-06 - Study of coke and deactivation over H-Beta zeolite
Z Zhu, T. Ruan, Q. Chen, W. Chen and D. Kong
271
24-P-07- Photoionization of N-alkylphenothiazines in transition-metal-ion modified mesoporous silica SBA-15 molecular sieves
Z. Luan and L. Kevan
271
24-P-08 - Potential use of AIMCM-41 for activation of metallocene catalyst
T. Sano, T. Niimi, T. Miyazaki, S. Tsubaki, Y. Oumi and T. Uozumi
271
24-P-09 - Activation of butanes with olefins carbenium cations over zeolite catalysts
S.E. Dolinsky and V.A. Plakhotnik
272
24-P-10 - Immobilization and mobilization of surface species during transformation of ethylene over HZSM-5 catalysts
Ziktinovgt, M. Ko~iHk, M. Derewihski, P. Sarv, J. Dubsk~, P. Hudec and A. SmieJkovd
272
24-P-11 - Zeolite-L as support of Fe microcystals for the Fischer-Tropsch synthesis
M.V. Cagnoli, N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, A.A. Yeramian and S. G. Marchetti
272
24-P-12 - Nb- and Ti-containing silica-based mesoporous molecular sieves as catalysts for photocatalytic oxidation of methane
J. Xin, X. Chen, J. Suo, Xia. Zhang, L. Yan and Shuben Li
273
24-P-13 - Catalytic properties of micelle templated microporous and mesoporous materials for the conversion of low-density polyethylene
J. Aguado, D.P. Serrano, R. Van Grieken, J.M. Escola and E. Garagorri
273
24-P-14 - Epoxidation of propylene in fixed bed reactor using supported titanium silicalite catalyst
X.S. Wang, Gang Li, H.S. Yan and X. W. Guo
273
24-P-15 - Acetylene and alkene oligomerization on ETS-10 having induced Bronsted acidity
A. Zecchina, C. Paz& C. Otero Aredn, G. Turnes Palomino, F.X. Llabr& i Xamena and S. Bordiga
274
lxiv 24-P-16 - Isomerization of n-butane over small crystals of H-Beta and Pt-H-Beta zeolite catalysts N. Kumar, M. Vaini, V. Nieminen, R. Byggningsbacka, L.-E. Lindfors, T. Salmi, D. Yu. Murzin and E. Laine
274
24-P-17 - Ethylene oligomerization with nickel-containing NaX zeolite M.O. de Souza, F.M.T. Mendes, R.F. de Souza, J.H. Z. dos Santos, L. Caumo, V. Conz, F. Majolo and L. V. Barbosa
274
24-P-18 - Studies of the methanol to hydrocarbons reaction using isotopic labeling: mounting evidence for a hydrocarbon pool mechanism S. Kolboe
275
24-P-19 - Formation and reactivity of alkoxy species through the reaction of alkylhalides with metal-exchanged zeolites R.J. CorrOa and C.J.A. Mota
275
24-P-20 The use of ITQ-7 as catalyst for alkylation of isobutane with 2-butene A. Corma, M.J. Diaz-Cabaftas, C. Martinez and S. Valencia
275
24-P-21 Butene isomerization over ferrierite and SUZ-4 zeolite V.L. Zholobenko and C.L.T. Stevens
276
24-P-22 - Volatile products of the conversion of cyclohexene over AI-MCM-41 M. Rozwadowski, M. Lezanska, J. Wloch, K. Erdmann, G. Zadrozna and J. Kornatowski
276
24-P-23 M. Laniecki
276
-
-
-
C u - Y
zeolite catalysts for methanol and ethanol steam reforming
24-P-24 - Hexenes obtaining on the nickel - ion exchanged zeolites M.K. Munshieva
277
24-P-25 - Catalytic sites of mesoporous silica in degradation of polyethylene A. Satsuma, T. Ebigase, Y. Inaki, H. Yoshida, S. Kobayashi, Md.A. Uddin, E Sakata, and T. Hattori
277
24-P-26 - The nature of medium acidity in [CuO/ZnO/ZrO2]SAPO-34 hybrid catalyst for CO2 hydrogenation: the study of the interactions between metal oxides and acid sites in zeolite S.-K. Ihm, S.-W. Back, Y.-K. Park and K.-C. Park
277
24-P-27 - Reaction pathways for the aromatization of cyclohexane and cyclohexene on Zn/H-ZSM-5 zeolites A. Urdgt, G. Telbiz and I. Sgmdulescu
278
lxv 24-P-28 - Coke species and coking mechanism of SAPO-34 in MTO process
Y. Qi, G. Wang, Z. Liu, L. Xu, X. Gao and W. Cui
278
24-P-29 - Pt-2,2'bipyridine complex encapsulated in Y zeolite - catalysts for ethylene selective dimerization
R. Zavoianu and E. Angelescu
278
24-P-30 - Aromatics formation from C4-C4- technical fraction over zinc- and zinc/copper-containing ZSM-5 zeolites
N. Bilba, Gh. Iofcea, 1. Asafiei, D.M. Padurariu and C.C. Pavel
279
24-P-31 - Aromatization of mixed-C4 hydrocarbons over the HZSM-5 catalysts modified by Zn and Ni cations
L. Wei, J.Z. Gui, H.S. Ding, X.T. Zhang, H.Y. Li, L. Song, Z.L. Sun and L. V.C. Rees
279
25 - C o n v e r s i o n of A r o m a t i c s
25-0-01 - Shape-selective methylation of 4-methybiphenyl into 4,4'dimethybiphenyl over modified ZSM-5 catalysts
J.-P. Shen, L. Sun and C. Song
151
25-0-02 - Facile Friedel-Craft's alkylation of phenol with 4-hydroxybutan-2-one over 13 and Y zeolites to produce raspberry ketone
K.K. Cheralathan, 1.S. Kumar, B. Arabindoo, M. Palanichamy and V. Murugesan
152
25-0-03 - Selective alkylation of naphthalene to 2,6-dimethylnaphthalene catalyzed by MTW zeolite
G. Pazzuconi, G. Terzoni, C.Perego and G. Bellussi
152
25-0-04 - Transalkylation reaction of phenol with trimethylbenzenes over Y and EMT zeolites
V. Hulea, 1. Fechete, P. Caullet, H. Kessler, T. Hulea, C. Chelaru, C. Guimon and E. Dumitriu
152
25-0-05 - Benzene alkylation with alkanes over modified MFI catalysts
A. V. Smirnov, E. V. Mazin, O.A. Ponomoreva, E.E. Knyazeva, S.N. Nesterenko and 1.1. Ivanova
153
25-P-06 - Isopropylation of napthalene over large pore zeolites
R.K. Ahedi, S. Tawada, Y. Kubota and Y. Sugi
280
25-P-07 - Shape-selective tert-butylation of biphenyl over HM, HY and HI3 zeolites in the liquid phase
D. Mravec, J. Horniakovd, M. Krdlik, M. Hronec, J. Joffre and P. Moreau
280
lxvi 25-P-08 - 1-Acetyl-2-methoxynaphthalene isomerization over zeolites. Effect of pore structure. V. Moreau, E. Fromentin, P. Magnoux and M. Guisnet
280
25-P-09 - Alkylation of phenol with propylene over solid acid catalysts B. Wang, C. W. Lee, T.-X. Cai and S.-E. Park
281
25-P-10 - Transalkylation of trimethylbenzene with toluene over large pore zeolites J. Cejka, A. Krejdi and J Hanika
281
25-P-11 - Physicochemical characterization and catalytic activity of A1-HMS for N-methylation of aniline JM. Campelo, A. Garcia, D. Luna, J.M Marinas, A.A. Romero and J.J. Toledano
281
25-P-12 - Catalytic activity of secondary aluminated mesoporous molecular sieve A1MCM-41 in the Friedel-Crafis reaction of bulky aromatic compounds H. Hamdan, A.B. Kim and M.N. Mohd Muhid
282
25-P-13 - Naphthalene alkylation with methanol employing solid catalysts J. Aguilar-P, A. Corma, J.A. de los Reyes, L. Noreha, G. Muhoz, J.M. Sanchez, A. Torales and I. Herndndez
282
25-P-14 - Alkylation of biphenyl and naphthalene with propene. Is zeolite Beta a shape-selective catalyst? D.M. Roberge and W.F. Holderich
282
25-P-15 - Alkylation of benzene by propane with participation of space divided centres S.I. Abasov, R.R. Zarbaliyev, G.G. Abbasova, D.B. Tagiyev and M.I. Rustamov
283
25-P-16 - Alkylation of isopropylnaphthalene over heteropoly acid catalysts supported on mesoporous materials M-W. Kim, W.-G. Kim, J.-H. Kim, Y. Sugi and G. Seo
283
25-P-17 - Highly selective isopropylation of xylenes catalyzed by zeolite Beta C.R. Patra, S. Kartikeyan and R. Kumar
283
26 - Catalysis for Oil Refining
26-0-01 - The isomerization selectivity in FCC process L.-J. Yan, M-Y. He, J. Fu and J. Long
158
26-0-02 - Design of zeolite catalyst for paraffin isomerisation J. Hou~vidka, C.J.H. Jacobsen and I. Schmidt
158
26-0-03 - Cyclohexane ring opening on metal-zeolite catalysts T.V. Vasina, O.V. Masloboishchikova, E.G. Khelkovskaya-Sergeeva, L.M. Kustov and P. Zeuthen
159
lxvii 26-0-04 Selective ring opening of naphthenic molecules M. Daage, G.B. Mc Vicker, M.S. Touvelle, C. W. Hudson, D.P. Klein, B.R. Cook, J.G. Chen, S. Hantzer, D.E.W. Vaughan and E.S. Ellis
159
26-0-05 - Reforming of FCC heavy gasoline and LCO with novel borosilicate zeolite catalysts C. Y. Chen and S.I. Zones
159
26-P-06 - Hydroisomerization of n-decane in the presence of sulfur. Effect of metal-acid balance and metal location L.B. Galperin, S.A. Bradley and T.M. Mezza
301
26-P-07 - Hydrodesulfurization of benzothiophene over noble metals supported on mesoporous silica MCM-41 M. Sugioka, A. Seino, T. Aizawa, J.K.A. Dapaah, Y. Uemichi and S. Namba
301
26-P-08 - Catalytic functionalities of USY zeolite supported hydrotreating catalysts K.S. Rawat, M.S. Rana and G. Murali Dhar
301
26-P-09 - Highly active, selective and stable ferrierite-based catalysts for the skeletal isomerization of n-C5-C7 C.P. Nicolaides, J. Makkonen and M. Tiitta
302
26-P-10 - Producing synthetic steamcracker feed from cycloalkanes (or aromatics) on various zeolite catalysts A. Raichle, H. Scharl, Y. Traa and J. Weitkamp
302
26-P-11 - n-Heptane hydroconversion and methylcyclohexane cracking as model reactions to investigate the pore topology of Nu-88 zeolite. S. Lacombe, A. Patrigeon and E. Benazzi
302
26-P-12 - New Mo and NiMo hydrodesulfurization catalysts supported on AIMCM-41. Effect of the support Si/A1 molar ratio T. Klimova, M. Calder6n and J. Ramirez
303
26-P-13 - Hydrogenation and ring opening of mono- and diaromatics for Diesel upgrading on Pt/Beta catalysts M.A. Arribas, J.J. Mahiques and A. Martinez
303
26-P-14 - Hydro denitrogenation activity of N i O - MoO3 catalysts supported on various mesoporous alumino silicates K. Shanthi, N.R. Sasi Rekha, R. Moheswari and T. Sivakumar
303
26-P-15 - Model hydrocracking catalysts combining NiMo sulfide and large-pore zeolite: effect of the zeolite nature on the location of NiMo sulfide in relation with catalytic properties J. Leglise, D. Cornet, M. Badlala, C Potvin and J.-M. Manoli
304
-
Ixviii 26-P-16 - Effect of zeolite acidity characteristics on the deactivation behavior of bifunctional large-pore zeolite catalysts during cyclopentane hydroconversion S. Gopal and P G. Smirniotis
304
26-P-17 - Characterization and catalytic activities of MCM-41 supported WS2 hydrotreating catalysts T. Chiranjeevi, P. Kumar, M.S. Rana, G. Murali Dhar and T.S.R. Prasada Rao
304
26-P-18 - Isomerization and hydrocracking of n-heptane and n-decane over bifunctional mesoporous molecular sieves C. Bischof and M. Hartmann
305
26-P-19 - Isomerization of cyclohexane, n-hexane and their mixtures on zeolite catalyst A. Holl6, J. Hancs6k and D. Kall6
305
26-P-20 - Application of adsorption Dubinin-Radushkevich equation for study of n-pentane and m-xylene conversion catalysts microporous structure S.B. Agayeva, B.A. Dadashev, S.I. Abasov and D.B. Tagiyev
305
26-P-21 - Hydroisomerization of n-hexadecane over Pt/A1-MCM-41 catalysts: two different A1 incorporation methods K.-C. Park and S.-K. Ihm
306
26-P-22 - Zr-containing hexagonal mesoporous silicas as supports for hydrotreating catalysts N.G. Kostova, A.A. Spojakina, L.A. Petrov, O. Solcova and K. Jiratova
306
26-P-23 - New catalysts for isomerization of long-chain n-paraffins M.I. Levinbuk, L.M. Kustov, T.V. Vasina, O.V. Masloboishchikova, M.L. Pavlov, I.E. Gorbatkina and V.A. Khavkin
306
27 - Selective
Oxidation
and Sulfur Resistance
27-0-01 - Singular catalytic properties of Ti-MWW in the selective oxidation of alkenes P. Wu, T. Komatsu, T. Yashima and T. Tatsumi
165
27-0-02 - Epoxidation of propylene over T S - 1 containing trace aluminum X. Guo, Xi. Wang, Min Liu, Gang Li, Yo. Chen and J. Xiu
165
27-0-03 - One step benzene oxidation to phenol using N20 over acid zeolites G. Juttu and R.F. Lobo
165
27-0-04 - Dual pathways for benzene hydrogenation on Pt/mordenites: implication for sulfur tolerance L. Simon, J.G. van Ommen, A. Jentys and J.A. Lercher
166
lxix 27-0-05 - Sulfur resistance of PtPd catalysts: preparation, characterization and catalytic testing K. Thomas, C. Binet, T. Chevreau, D. Cornet and J.-P. Gilson
166
27-P-06 - Microporous metallosilicates for the oxidation of hydrocarbons: preparation, characterization and catalytic activity U. Arnold, R.S. da Cruz, D. Mandelli and U. Schuchardt
365
27-P-07 - High catalytic activity of Fe(III)-substituted aluminophosphate molecular sieves (FeAPO) in oxidation of aromatic compounds X. Meng, Y. Yu, L. Zhao, J. Sun, K. Lin, M. Yang, D. Jiang, S. Qiu, and F.-S. Xiao
365
27-P-08 - Selective oxidation of propyl alcohols over zeolites modified with cations of the transition metals A.M. Aliyev, D.B. Tagiyev, S.M. Medzhidova, S.S. Fatullayeva, A.R. Kuliyev, T.N. Shakhtakhtinsky, G.A. Ali-zade and K.1. Matiyev
365
27-P-09 - Niobium leaching from the catalysts applied in the sulfoxidation of thioethers with hydrogen peroxide M. Ziolek, A. Lewandowska, M. Renn, 1. Nowak, P. Decyk and J. Kujawa
366
27-P-10 - Biomimetic oxygen transfer by Co and Cu complexes immobilized in porous matrices K. Hernadi, I. P6link6, E. BOngyik and I. Kiricsi
366
27-P-11 Titanium molecular sieves convert hydrogen peroxide into 102 F.M. van Laar, D.E. De Vos, P. Grobet, J.-M. Aubry, L. Fiermans and P.A. Jacobs
366
27-P-12 - Propane oxidation on Cu/ZSM-5 catalyst: the effect of copper and aluminum content in the reducibility and in the activity of Cu active species M.S. Batista and E.A. Urquieta-Gonz6lez
367
27-P- 13 - Oxidizing conversion of isobutanol on zeolites S. Zulfugarova
367
27-P-14 - Photocatalytic production of H202 over heterogenized quinone in zeolite J.S. Hwang, C.W. Lee, H.S. Chai and S.-E. Park
367
27-P-15 - Liquid-phase oxidation of cyclohexane in the presence of chromium and iron ETS-10 materials A. Valente, P. Brand, o, Z. Lin, F. Gonqa!ves, 1. Portugal M. W. Anderson and J. Rocha
368
27-P- 16 - Effect of oxygen concentration on catalyst deactivation rate in vapor phase Beckmann rearrangement over acid catalysts T. Takahashi and T. Kai
368
-
lxx 27-P-17 - On the role of the titanium active site in the phenol/anisole hydroxylation over titanium substituted crystalline silicates
U WilkenhOner, D.W. Gammon and E. van Steen
368
2 8 - Confinement and Physical Chemistry for Catalysis 28-O-01 - Reactivity enhancement by molecular traffic control - a consequence of released single-file constraints
P. Brgiuer and J. Kcirger
173
28-0-02 - Aromatization of n-hexane over ZnNi/HZSM-5 catalyst induced by microwave irradiation
J.Z Gui, H.S. Ding, N.N. Liu, Y.R. Gao, Z.L. Cheng, X.T. Zhang, B. Ma, L. Song, Z.L. Sun and L. V.C. Rees
173
28-0-03 - Artificial photosynthesis using zeolites
N. Castagnola and P.K. Dutta
174
28-0-04 - Synthesis of macrocycles using molecular sieve catalysts
3/1. Radha Kishan, N. Srinivas, S.J. Kulkarni, M. Ramakrishna Prasad, G. Kamalakar and K. V. Raghavan.
174
28-0-05 - Effect of single-file diffusion on the hydroisomerization of 2,2dimethylbutane on platinum loaded H-mordenite
F.J.M.M. de Gauw, J. van Grondelle and R.A. van Santen
174
28-P-06 - Use of coke-selectivated H-ZSM-5 in xylene isomerization
E Bauer and A. Freyer
307
28-P-07 - Photocatalytic reactions on chromium containing mesoporous molecular sieves under visible light irradiation: decomposition of NO and partial oxidation of propane
H. Yamashita, K. Yoshizawa, M. Ariyuki, S. Higashimoto and M. Anpo
307
28-P-08 - Enhancing the shape selectivity ofnanocrystalline HZSM-5 zeolite v/a comprehensive modifications
H.C. Guo, X S. Wang and G.R. Wang
307
28-P-09 - Nature of shape-selective catalysis in the ethylation and the isopropylation of biphenyl over H-mordenites
Y. SugL S. Tawada, T. Sugimura, Y. lmada, Y. Kubota, T. Hanaoka and T. Matsuzaki
308
28-P-10 - Adsorption of selected amino acids from aqueous solutions on mesoporous molecular sieves
S. Ernst, M. Hartmann and S. Munsch
308
lxxi 28-P-11 - Influence of OH groups of Beta zeolites on the synthesis of MTBE
F. Collignon and G. Poncelet
308
28-P-12 - About a possibilities of effectiveness increasing of porous catalyst granules with controlled activity profile
V. V. Andreev
309
28-P-13 - Effects of channel structures of wide pore zeolites on m-cresol transformation
F. L6pez, L. Gonzdtlez, J.C. Herndmdez, A. Uzc6tegui, F.E. Imbert and G. Giannetto
309
28-P-14 - A study on the use of zeolite Beta as solid acid catalyst in liquid and gas phase esterification reactions. The influence of the hydrophobicity of the catalyst
M.J. Verhoef R.M Koster, E. Poels, A. Bliek, J.A. Peters and H. van Bekkum
309
28-P-15 - The influence of pore geometry on the alkylation of phenol with methanol over zeolites
G. Moon, K.P. MOller, W. BOhringer and C.T. O'Connor
310
28-P-16 - Diffusion analysis of cumene cracking over ZSM5 using a jetloop reactor
P. Schwan and K.P. MOller
310
2 9 - New Approaches to Catalyst Preparation 29-0-01 - The catalytic performance of zeolite ERS-10
C. Perego, M. Margot& L. Carluccio, L. Zanibelli and G. Bellussi
178
29-0-02 - Towards total hydrophobisation of MCM-41 type silica surface
T. Martin, A. Galarneau, D. Brunel, V. lzard, V. Hulea, A.C. Blanc, S. Abramson, F. Di Renzo and F. Fajula
178
29-0-03 - Novel Lewis-acid catalysts (NLACs): their properties, characterisation and use in catalysis
M.H. Valkenberg, C. deCastro and W.F. Hoelderich
179
29-0-04 - A controlled dispersion of A13+ onto a silica mesoporous material. A comparative study with A13+ mcorporation. •
O. Collart, A. Galarneau, F. Di Renzo, F. Fajula, P. Van Der Voort and E. F. Vansant
179
29-P-05 - Catalytic properties of MFI zincosilicates
S. Kowalac, E. Szymkowiak, 1. Lehmann and G. Giordano
311
lxxii 29-P-06 - Acidity characterization of dealuminated H-ZSM-5 zeolites by isopropanol dehydration C.S. Triantafillidis, V.A. Tsiatouras, A.G. Vlessidis and N.P. Evmiridis
311
29-P-07 - Acidic ZrO2/SO4 2" in mesoporous materials Y. Sun, L. Zhu, H. Lu, D. Jiang and F.-S. Xiao
311
29-P-08- HMS catalysts containing transition metals or transition metal complexes Z. Fu, Du. Yin , W. Zhao, Y. Chen, Do. Yin, J. Guo, C. Xiong and Luxi Zhang
312
29-P-09 -Synthesis of hydrophobic mesoporous molecular sieves by surface modification K.-K. Kang and H.-K. Rhee
312
29-P-10 - Guanidine catalysts supported on silica and micelle templated silicas: new basic catalysts for organic chemistry D.J. Macquarrie, D. Brunel, G. Renardand A. C. Blanc
312
29-P-11 - Texture of dealuminated mordenite catalysts modified with cerium and catalytic properties in the isopropylation of biphenyl M. Krdlik, J. Horniakova, D. Mravec, V. Jorik, M. Michvocik and P. Moreau
313
29-P-12 - Partially crystalline zeolitic material as novel solid acid catalysts Ming Liu, Z. Li, S. Lou, Q Wang and S. Xiang
313
29-P-13 - Novel mesoporous carbon as a catalyst support for Pt and Pd for liquid phase hydrogenation reactions W.S. Ahn, K.1. Min, Y.M. Chung, H.-K. Rhee, S.H. Joo and R. Ryoo
313
29-P-14 - Investigation of catalytic activity of framework and extraframework cobalt and manganese in MeAPO-34 prepared from fluoride medium A. Ristik, G. Avgouropoulos, T. Ioannides and V. Kaudid
314
29-P-15 - Preparation and characterization of bimetallic Pt-Zn catalysts supported on zeolite NaX J. Silvestre-Albero, F. Coloma, A. Sepfilveda-Escribano and F. RodriguezReinoso
314
29-P-16 - Surface modification of the uncalcined acid'made mesoporous silica materials in a one-step procedure H.-P. Lin, Y.-H. Liu, C.-P. Kao, S.-B. Liu and C.-Y. Mou
314
29-P-17 - Zirconia nanoparticles in ordered mesoporous material SBA-15 J. Sauer, S. Kaskel, M. Janicke and F. Schath
315
lxxiii 29-P-18 - Preparation using ozone treatment, characterization and application of isomorphously substituted Ti-, V- and Zr-MCM-41 catalysts D. Mdhn, J. Haldsz, E. Meretei, Z. K6nya, A. Fonseca, J. B.Nagy and 1. Kiricsi
315
29-P-19 - Preparation and catalytic evaluation of [Ga]MCM-58 and of MCM-58type catalysts with different aluminum contents S. Ernst, M. Hartmann, T. Hecht and A. Weber
315
29-P-20- IR study on the reaction path of methanol decomposition over basic zeolites M. Rep, J.G. van Ommen, L. Lefferts and J.A. Lercher
316
29-P-21 - Synthesis and characterization of highly ordered mono- and bimetallic substituted MCM-41 molecular sieves and their catalytic properties in selective oxidation of hydrocarbons V. Pdrvulescu, C. D~tscalescu and B.L. Su
316
29-P-22 - On the direct synthesis of noble metal cluster containing MCM-41 using surfactant stabilised metal nanoparticles A.B.J. Arnold, J.P.M. Niederer, W.F. Hoelderich, B. Spliethof B. Tesche, M. Reetz and H. Boenneman
316
29-P-23 - Microporous zincophosphates as solid base catalysts L.A. Garcia-Serrano, T. Blasco, J. Pdrez-Pariente and E. Sastre
317
29-P-24 - Zirconium containing AI-MCM-41- synthesis, characterisation and catalytic performance in 1-hexene isomerisation I. Eswaramoorthi, V. Sundaramurthy and N. Lingappan
317
29-P-25 - Iron containing zeolites and mesoporous silica as sulfuric acid catalyst A. Wingen, W. Schmidt, F. Schiith, A.C. Wie, C.N. Liao and K.J. Chao
317
29-P-26 - Deep-bed dealumination of ZSM-5 zeolites: changes in structure and catalytic activity P. Hudec, A. Smiegkovdl, Z Zidek, L. Sabo and B. Liptdkovd
318
29-P-27 - Fabrication of honeycomb structures with powder MCM-48 silica Y.-S. Ahn, M.-H. Han, S. Jun and R. Ryoo
318
29-P-28 - Acidic hybrid catalysts prepared by grafting large-pore silica M41S materials B. Lindlar, M. Lachinger, M. Haouas, A. Kogelbauer and R. Prins
318
29-P-29 - Preparation of tungsten carbide supported on (A1-)FSM-16 and its catalytic activity M. Nagai, K. Kunieda, S. Izuhal and S. Omi
319
lxxiv 29-P-30 - Ti-MCM-48 with different titanium loading: synthesis, spectroscopic characterization and catalytic activity
V. Dellarocca, M.L. Pe~a, F. Rey, A. Corma, S. Coluccia and L. Marchese
319
29-P-31 - Comparison of 3-aminopropylsilane linked to MCM-41 and HMS type silicas synthesised under biphasic and monophasic conditions
D.J. Macquarrie, M. Rocchia, B. Onida, E. Garrone, P. Lentz, J. B.Nagy, D. Brunel, A.C. Blanc and F. Fajula
30- Environmental
319
Catalysis
30-0-02 - Characterization and performance of ex-framework FeZSM-5 in catalytic N20 decomposition
J. Pdrez-Ramirez, G. Mul, F. Kapteijn, 1. W.C.E. Arends, A. Ribera and J.A. Moulo'n
172
30-O-03 - Effect of carbon number in hydrocarbon reductant on the selective catalytic reduction of NO over cation-exchanged MFI zeolites
A. ShichL Y. Kawamura, A. Satsuma and T. Hattori
172
30-0-04 - The temperature-dependent storage of NOx on metal-containing zeolites under dry and wet conditions
R. Fricke, M. Richter, E. Schreier, R. Eckelt and H. Kosslick
172
30-0-05 - Catalytic destruction of chlorinated VOCs.- Influence of characteristics of Pt/HFAU catalysts on the destruction of dichloromethane
L. Pinard, J. Tsou, P. Magnoux and M. Guisnet
173
30-P-06 - Effect of the reductant nature on the catalytic removal of N20 on a Fezeolite-Beta catalyst
G. Delahay, M. Mauvezin, B. Coq and S. Kieger
320
30-P-07 - Degradation of N-nitrosamines on zeolites
J.H. Zhu, B. Shen, Y. Xu, J. Xue, L.L. Ma and Q.H. Xu
320
30-P-08 - ZrO2/NaY: a new material for removal of N-nitrosamines pollution
J.H. Zhu, J.R. Xia, Ying Wang, G. Xie, J. Xue and Y. Chun
320
30-P-09 -Total oxidation of n-pentane, cyclohexane and their mixtures on the Cu-containing ZSM-5 zeolites
M.A. Botavina, IV. V. Nekrasov and S.L. Kiperman
321
30-P-10 - Modified natural zeolite in catalytic clearing of exhaust and ejected gases from nitric and carbon oxides
L. Akhalbedashvili and Sh. Sidamonidze
321
lxxv 30-P-11 - Selective catalytic reduction of N20 with light alkanes over different Fe-zeolite catalysts S. Kameoka, S. Tanaka, K. Kita, T. Nobukawa, S. Ito, T. Miyadera and K. Kunimori
321
30-P-12 - Selective catalytic reduction of NOx by NH3 over Mn supported MCM-41 mesoporous materials E.E. Iojoiu, P. Onu, S. Schmitzer and W. Weisweiler
322
30-P-13 - Transition metal exchanged-MCM-22 catalysts for N20 decomposition A.J.S. Mascarenhas, H.M.C. Andrade and H.O. Pastore
322
30-P-14 - The NO and N20 selective catalytic reduction on copper and iron containing ZSM-5 catalysts: a comparative study G. Fierro, G. Ferraris, M. Inversi, M. Lo Jacono and G. Moretti
322
30-P-15 - A comparison of different preparation methods of indium-modified zeolites as catalysts for the selective reduction of NO C. Schmidt, T. Sowade, F.-W. Schutze, 14. Berndt and W. Granert
323
30-P- 16 - Local structures of Ag+/ZSM-5 catalysts and their photocatalytic reactivity for the decomposition of N20 into N2 and 02 M. Matsuoka, W.-S. Ju and M. Anpo
323
30-P-17 - One stage catalytic cracking of plastic waste on zeolitic catalysts K. Gobin, D. Koumantaropoulos and G. Manos
323
30-P-18 - Analysis of the deep catalytic oxidation of binary CVOCs mixtures over H-ZSM-5 zeolite R. L6pez-Fonseca, J.I. Guti&rez-Ortiz, A. Aranzabal and J.R. Gonz6lez-Velasco
324
30-P-19 - Solid state MAS NMR studies of zeolites and alumina reacted with chlorofluorocarbons (CC12F2, CHC1F2) I. Hannus, Z K6nya, P. Lentz, J. B.Nagy and I. Kiricsi
324
30-P-20 - Zeolite-containing photocatalysts for treatment of waste-water from petroleum refineries A.K. Aboul-Gheit and S.M. Ahmed
324
30-P-21 . Autoreduction of C u 2+ species in Cu-ZSM-5 catalysts studied by diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry and elemental analysis G. Moretti, G. Ferrarbx and P. Galli
325
30-P-22 - Performance of bi-and tri-metallic mordenite catalysts for the lean SCR of NOx by methane F. Bustamante, P. A vil and C. Montes de Correa
325
lxxvi 30-P-23 - Total oxidation of volatile organic compounds - catalytic oxidation of toluene over CuY zeolites
A.P. Antunes, J.M. Silva, M.F. Ribeiro, F.R. Ribeiro, P. Magnoux and M. Guisnet
325
30-P-24 - Study on relationship between the local structures of Ti-HMS mesoporous molecular sieves and their photocatalytic reactivity for the decomposition of NO into N2 and 02
J. Zhang, B. He, M. Matsuoka, H. Yamashita and M. Anpo
326
30-P-25 - Influence of synergistic effects on the selective catalytic reduction of NO× with CnHm over zeolites
S.N. Orlik and V. L. Struzhko
326
30-P-26 - Catalytic properties of Fe-Co double layered hydroxides synthesised with Beta zeolite for toluene oxidation
J. Carpentier, S. Siffert, J.F. Lamonier and A. Aboukags
326
30-P-27 - Selective catalytic reduction of NO over Fe z e o l i t e s - catalytic and in-
s i t u - DRIFTS studies F. Heinrich, E. LOftier and W. Grunert
327
30-P-28 - Selective catalytic reduction of NO by methane over AgNaZSM-5 catalysts in the excess of oxygen
C. Shi, M. Cheng, Z Qu, X. Yang and X. Bao
327
30-P-29 - ZSM-5/Raney Fe composite used as DeNO× catalyst
B. Zong, W. Wang, L. Lu and X. T. Shu
327
30-P-30 - Reduction of nitric oxide by hydrocarbons on Ni-ion exchanged zeolites
B.I. Mosqueda-Jim~nez, M. Brandmair, A. Jentys, K. Seshan and J.A. Lercher
328
30-P-31 -NOx Reactivity on microporous MeAPOs. Spectroscopic and catalytic studies
A. Frache, M. Cadoni, S. Coluccia, L. Marchese, B. Palella, R. Pirone and P. Ciambelli
328
30-P-32 - Adsorption characteristics on zeolite catalysts for hydrocarbon removal under cold-start engine condition
H.K. Seo, J. W. Oh and S.J. Choung
328
30-P-33 - In-situ synthesized ZSM-5 on cordierite substrate and NO decomposition on the monolithic catalysts
N. Guan, X. Shan, X. Zeng, S. Liu, S. Xiang, U. Illgen and M. Baerns 30-P-34
-
329
Selective reduction of NO to N2 in the presence of oxygen
T. Furusawa, K. Seshan, S.E. Maisuls, J.A. Lercher, L. Lefferts and K. Aika
329
lxxvii 30-P-35 - Catalytic behaviour of Co-exchanged ferrierite for lean NOx-SCR with methane
D. Sannino, M. Concetta Gaudino and P. Ciambelli
329
31 - E n v i r o n m e n t - F r i e n d l y Applications of Zeolites
31-O-01 - Influence of Jordanian chabazite-phillipsite tuff on nutrient concentration and yield of strawberry
K.M. Ibrahim, A.M. Ghrir and 14.N. Khoury
181
31-O-02 - Improvements in yield and quality of crops with NASA zeoponic fertilizer delivery systems: turf, flowers, vegetables and grain
R.D. Andrews and S.B. Kimi
181
31-O-03 - Fe/MFI as a new heterogeneous Fenton-type catalyst in the treatment of wastewater from agroindustrial processes
G. Centi, S. Perathoner and G. Romeo
181
31-O-04 - Investigation of the storage properties of zeolites and impregnated silica for thermochemical storage of heat
J. Jcinchen, ,4. Grimm and H. Stach
182
3 l-P-05 - Application of sorbing composites on natural zeolite basis for heavy metals contaminated territories rehabilitation
W. Sobolev, V. llyin, F. Bobonich and S. Bdrdny
369
3 l-P-06 - Investigation of lead removal from wastewater by Iranian natural zeolites using 2~2pb as a radiotracer
H. Kazemian, P. Rajec, F. Macasek and J. O. Kufacakova
369
3 l-P-07 - Purification of the waste liquid hydrocarbons using cation-exchanged forms of clinoptilolite
M.Kh. Annagiyev, S.G. Aliyeva and T. M.Kuliyev
369
3 l-P-08 - The use of transcarpathian zeolites for concentrating trace contaminants in water
V. O. Vasylechko, L. O. Lebedynets, G. V. Gryshchouk, Yu.B. Kuz 'ma, L.O. Vasylechko and V.P. Zakordonskiy
370
3 l-P-09 - Ammonia removal from drinking water using clinoptilolite and Lewatit S 100
H.M. Abd El-Hady, A. Grtinwald, K. Vlckova and J. Zeithammerova
370
3 l-P-10 - Pilot plant of ammonium removal from nitrogen industry waste waters by an Ukrainian clinoptilolite
Yu.I. Tarasevich and V.E. Polyakov
370
lxxviii 3 l-P-11- Croatian clinoptilolite and montmorillonite-rich tufts for ammonium removal
M. Rozic and S. Cerjan-Stefanovic
371
3 l-P-12 - Ammonia removal from water by ion exchange using South African and Zambian zeolite samples, and its application in aquaculture
M. Mwale and H. Kaiser
371
3 l-P- 13 - Permanent storage of chromium in hardened FAU-type zeolite/cement pastes
C. Colella, D. Caputo and B. de Gennaro
371
3 l-P-14 - Phosphorus removal from wastewater in upgraded activated sludge system with natural zeolite addition
J. Hrenovic, Y. Orhan, H. BiiyfikgfingOr and D. Tibljad
372
3 l - P - 1 5 - Application of natural zeolites to purify polluted river water
M. Okamoto and E. Sakamoto
372
3 l-P-16 - Elimination of ammonium in seawater by zeolitic products
J.M. Lopez-Alcalgl andJ.L. Lopez-Ruiz
32 - Zeolite Minerals
372
and Health Sciences
32-0-01 - Biomedical applications of zeolites
K. Pavelic, B. Subotic and M. Colic
170
32-0-02 - Zeolites and other porous materials in the toxicity of inhaled mineral dusts
I. Fenoglio, L. Prandi, M. Tomatis and B. Fubini
170
32-0-03 - Study of the reaction of a Ca-clinoptilolite and human bile
R. Sim6n Carballo, G. Rodriguez-Fuentes, C. Urbina and A. Fleitas
170
32-0-04 - In vitro adsorption of zearalenone by octadecyldimethylbenzyl ammonium-exchanged clinoptilolite-heulandite tuff and bentonite
A. Dakovic, M. Tomasevic-Canovic, V. Dondur, D. Stojsic and G. Rottinghaus
171
32-0-05 - Zeolites in sexual confusion: slow release of pheromones
J. Muftoz-Pallares, E. Primo, J: Primo and A. Corma
171
32-P-06 - Effects of dietary inclusion of natural zeolite on broiler performance and carcass characteristics
E. Christaki, P. Florou-Paneri, A. Tserveni-Gousi, A. Yannakopoulos and P. Fortomaris
373
lxxix 32-P-07 - Interaction studies between aspirin and purified natural clinoptilolite A. Rivera, L.M. Rodriguez-Albelo, G. Rodriguez-Fuentes and E. Altshuler
373
32-P-08 - Channel model for the theoretical study of aspirin adsorption on clinoptilolite: water influence A. Lam and A. Rivera
373
32-P-09 - In vitro and in vivo effect of natural clinoptilolite on malignant tumors M. Poljak Blazi, M. Katic, M. Kralj, N. Zarkovic, T. Marotti, B. Bosnjak, V. Sverko, T. Balog and K. Pavelic
374
32-P-10 - Effects of natural clinoptilolite-rich tuff and sodium bicarbonate on milk yield, milk composition and blood profile in Holstein cows A. Nikkhah, A.R. Safamehr and M. Moradi - Shahrbabak
374
32-P-11 - Effect of natural clinoptillolite-rich tuff on the performance of Varamini male lambs A. Nikkhah, A. Babapoor and M. Moradi- Shahrbabak
374
32-P-12 - Clinoptilolite and the possibilities for its application in medicine N. Izmirova, B. Aleksiev, E. Djourova, P. Blagoeva, Z Gendjev, Tz. Mircheva, D. Pressiyanov, L. Minev, T. Bozhkova, P. Uzunov, 1. Tomova, M. Baeva, A. Boyanova, T. Todorov and R. Petrova
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Studies in Surface Sbience and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
Ordered Mesoporous Materials - State of the Art and Prospects F. Schtith MPI ftir Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mtilheim, Germany
Research in ordered mesoporous oxides has increased dramatically in intensity over the last years. Developments not foreseen at the time when MCM-41 and FSM-16 were discovered have taken place, and in some cases applications of these materials are on the horizon. This paper will cover the discoveries which have expanded the scope of research in this field and try to give an outlook where new developments could take place. 1. I N T R O D U C T I O N When one searches for the key words (MCM-41 or FSM-16 or SBA-15 or ordered mesoporous oxides or ordered mesoporous materials) in the Web of Science, almost 1500 hits were reported in F e b r u a r y 2001, 450 and this set of key words w 400 c i i does not even give hits for .o 350 (g II all relevant publications, o 300 ,Q II since in the early = 250 12. i l l publications these materials ~ 2oo I I I I '- 150 were called "mesoporous I I I I molecular sieves". Research E 100 = l i l l E = 50 increased dramatically in __111111 the recent years: About half of the 1500 publications result from 1999 or 2000. year One might have expected t h a t after an initial phase Fig. 1: Development of publications on ordered on the synthesis and mesoporous oxides since 1990. characterization of such materials, by now the applications would have moved into the center of attention. However, this proved to be the case to a limited extent only. The synthesis and characterization had to offer so m a n y new aspects, that this still seems to be the most active area of research.
In the following the major achievements - seen from a personal perspective - of the last years in the field shall be highlighted, but it is not intended to give a comprehensive review. It will then be attempted to give a projection where the research on ordered mesoporous materials might move in the future. 2. S T R U C T U R E S
After initially FSM-16 [1] and MCM-41 [2] as the hexagonal members and MCM48 [3] as the cubic Ia3d member of the ordered mesoporous materials had been synthesized, a wide range of other structures became available quite rapidly, most of which had pure surfactant liquid crystal counterparts. Some, however, were unique structures only known for silica-surfactant composites. For the hexagonally ordered mesoporous silicas the route leading to the formation of SBA-15 [4] is the most exciting novel development after the discovery of the initial pathways. Before this discovery pore sizes of ordered mesoporous silica were limited to approximately 10 nm, as reported already in the initial papers, wall thickness was always found to be around 1 nm. The use of the triblockcopolymers of the Pluronics type expanded the accessible range dramatically. Substantially higher pore sizes and a wall thickness up to 6 nm could be achieved. The blockpolymer template can easily be removed by extraction or calcination, and the resulting material has a very good stability against water. After this initial publication, many other researchers used SBA-15 instead of MCM-41 type materials for further investigations. A serious problem in analyzing the structures of ordered mesoporous materials is, however, the fact that typically X-ray diffraction patterns are obtained which have only few reflections. Thus, often only space groups can be assigned, but no full structure solution is possible. So far, most structural models are just that, i.e. models, and they still have to be confirmed by either X-ray or electron crystallography. The 2-dimensionally ordered MCM-41 and the cubic MCM-48 have until recently probably been the two examples which were structurally well characterized by XRD and TEM [5,6]. One of the most notable developments, from the structure characterization point of view as well as with respect to the structure of the materials itself, was the structure solution of SBA-1, SBA-6, and SBA-16 with a novel electron crystallographic technique [7]. This technique uses the fact that the TEM image contains information both on the phase and the amplitude of the structure factors. To obtain the 3-D image of the structure, different 2-D projections of the structure are recorded with TEM. Fourier analysis of the images taken along different directions collectively provide information on the 3-D structure in reciprocal space. This data set can be backtransformed which eventually gives the 3-D real space structure. The technique allowed to gain surprisingly detailed insight into the structure of three different ordered mesoporous silicas. Both SBA-1 and SBA-6 have interesting bimodal pore size distributions. Both structures consist of a packing of differently sized A- and B-cages, the difference between the two being the dimensions of pores and walls. The pores ]n SBA-6 have sizes of 2 nm and 3.3 x 4.1 nm, resp., in
SBA-1 pore sizes are determined to be 0.2 nm and 1.5 x 2.2 nm, resp. The smaller pore size of the SBA-1 is not fully ascertained as yet, since sorption analysis suggests a somewhat bigger size for this type of pores. For SBA-16 a bcc packing of cavities with a diameter of 9.5 nm is determined, in which the cavities are connected by pores of 2.3 nm along the [111] directions. These bimodal size distributions of structural pores observed for SBA-1 and SBA-6 are unique for ordered mesoporous materials. The pore size distribution of SBA-15 is probably also bimodal, in which the bigger, hexagonally ordered structural pores determined by the surfactant are connected by micropores through the silica walls [8]. However, these micropores do not seem to be well ordered and are rather the result Fig. 2: a) Typical TEM of calcined of the fact, that part of the KSW-2 (pH 4.0) and the corresponding triblockcopolymer surfactant ED pattern indexed as hk0 projection. penetrates the silica. b) Typical TEM and the corresponding Another very remarkable structure ED pattern of as-synthesized KSW-2 was recently reported by the group of (pH 6.0). c) Another TEM of the as- Kuroda [9]. So far all structures with synthesized KSW-2 (pH 6.0). Arrows one dimensional pore systems were imply the observed place of the bending either hexagonally packed or of silicate sheets derived from disordered. Kuroda succeeded in kanemite, from ref. [9]. synthesizing a square packing of pores (Fig. 2) in an orthorhombic structure which are most probably formed following the folded sheet mechanism originally proposed for FSM-16. Formation of the material - called KSW-2 - is possible by strict pH control during the transformation of the kanemite-surfactant composite. 3. C O M P O S I T I O N S
The first ordered mesoporous materials reported were silicas or aluminumsilicates. The majority of all published investigations is still based on such compositions. In addition, many different elements, recently listed in a comprehensive review [10], have been introduced into the framework of ordered mesoporous oxides, just as in zeolitic frameworks. Such compositions could
become important in catalytic applications, similar to the progress made in zeolite chemistry, where, for instance, TS-1 was a major advance in oxidation chemistry over zeolites. Conceptually, however, the synthesis of fully nonsiliceous frameworks was the bigger step. The possibility to extend the approach had been predicted very early [5], and the first partial success was achieved in 1994, when several different non-siliceous materials were introduced [11]. However, all those materials were not stable upon template removal. The first stable compositions were synthesized in 1995 and 1996 as TiO2 [12] and ZrPxOy [13]. From then on many other materials were obtained, not only in a mesostructured, but also in a mesoporous form. Most of these, however, where rather disordered, and the highest degree of order is still observed in the titania and zirconia based materials. Non-siliceous mesoporous materials are reviewed in a recent review [14]. The majority of the hitherto reported non-siliceous mesoporous materials are hexagonally ordered or totally disordered. We recently reported a zirconium-based cubic mesostructure [15], which at that time could not be stabilized to result in a mesoporous material. Using the phosphate route developed previously for the stabilization of the hexagonal phase [13] we now also succeeded in obtaining a mesoporous cubic zirconium oxo phosphate (Fig. 3) [16]. Other non-hexagonal structures were prepared by the route to non-siliceous materials analogous to the synthesis of SBA-15 described by the Stucky group [17]. Other than for SBA-15, the synthesis is carried out in alcohol instead of aqueous solution. The pathway is remarkable, because it allows the synthesis of various different framework compositions and probably has the highest flexibility with respect to structure, pore sizes and composition of all preparations known so far. Amongst others, it is suitable for the preparation of a well ordered mesoporous cubic titania, as Fig.4: TEM of an SBA-15 sample demonstrated by XRD, sorption and loaded with 28wt.% of Y203. The TEM. coating of the walls is visible as the high contrast.
An alternative pathway to obtain essentially non-siliceous compositions was reported recently. This route relies on the fact, that some oxides spread under suitable conditions on silica. If a mesoporous silica is thus coated with a different oxide, a material with essentially the surface area of silica, but the surface functionality of the spreaded oxide results. This has been demonstrated for rare earth oxides [ 18], a TEM image of which is shown in fig. 4. More surprising than these non-silica oxides, however, was the discovery of nonoxidic compositions: Already relatively early it was shown that noble metals could be mesostructured and even obtained in mesoporous form using the true liquid crystal templating mechanism [19]. Later on, similar structures were obtained via a "nanocasting" route with SBA-15 as a mold and a volatile Pd-precursor [20]. After dissolution of the SBA-15 mesostructured Pd-particles were left. Another highly innovative development with respect to framework composition were the materials containing carbon or even consisting of pure carbon. Silicas with partly carbonaceous walls were pioneered by the groups of Inagaki [21], Stein [22] and Ozin [23]. The synthetic feature which allows introduction of the alkyl group as an integral part of the wall structure is the use of silicon precursors of the general type RO3Si-R-SiOR3 in which the alkoxy units are hydrolized and provide the linkage to other units, but the bridging alkyl is not attacked during mesostructure formation and remains in the material. Even more fascinating is the synthesis of purely carbonaceous ordered mesoporous materials. However, here the pathway is totally different. The "nanocasting" mentioned already above has in fact been pioneered for this class of Fig. 5: TEM image of an ordered materials, called CMK-1 [24]. A silica mesoporous carbon CMK-1 obtained with a 3-dimensional pores system (the from ,,nanocasting" in a MCM-48 micropores connecting the linear pores mold (top). SEM image of particles of in SBA-15 also provide for CMK-1 (bottom), from ref. [24]
threedimensionality in this respect) is impregnated with a suitable carbon precursor, for instance sucrose/H2SO4. The carbon precursor is pyrolized in the pore system and then the silica framework is removed by leaching with NaOH or HF. The remaining mesoporous carbon structure has remarkable textural features due to the low density of carbon, such as a surface area exceeding 1500 m2/g and specific pore volumes far above 1 ml/g. In addition, the mesopore structure as well as the morphology of the particles on a micrometer scale are surprisingly perfect (Fig. 5). 4. M A C R O S T R U C T U R E S
The products resulting from the early syntheses of mesoporous silica were typically finely divided powders with no well defined morphology. Soon, however, monoliths became available from the true liquid crystal templating route [25] and from 1996 on a wide variety of different shapes, including spheres, fibers, thin films, and many other more complex morphologies were reported, some of which were designed by the process conditions, such as emulsion templating or spin casting, some of which formed spontaneously by a self-organization process. These various morphologies are covered in a recent review [26] and shall not be discussed extensively here. However, one type of morphologies has very remarkable structural properties. These are the fibers and small particles formed spontaneously in the acidic quiescent system introduced by Huo et al. [27]. At the time of the discovery of these fibers the internal architecture was not clear, although there were indications that the channels would run parallel to the fiber axis [27]. However, recently in an elegant series of observations, the group of Marlow clarified the internal structure of the fibers [28,29]: The fibers have a circular internal structure, with the channels of the hexagonal mesostructure whirling around the fiber Fig. 6: TEM image of the fiber center axis (Fig. 6). The smaller particles with of an ordered mesoporous fiber circular or distorted circular symmetry taken perpendicular to the fiber axis reported in several publications probably on a microtomed sample, from ref. have a very similiar internal structure, [28]. which is, however, formed presumably from a slightly different kind of seed. This kind of internal organization raises several highly interesting questions, for instance concerning the mechanism of formation of such structures. Even more fascinating seems to be the fact that these ordered mesostructured fibers are a novel type for the organization of solid
matter. The objects are neither crystals (no translation periodicity) nor quasicrystals, but objects with a rotational type of symmetry, called circulites [30]. This leads to an altered reciprocal space, where the fibers are not represented as points, as a crystal would, but rather as complex ring structures. The altered reciprocal space structure is not just a mathematical construct, but has, for instance, consequences for the diffraction behavior of the fibers.
5. A P P L I C A T I O N S First obvious applications of ordered mesoporous materials were seen in catalysis, where a need for zeolite-like materials with bigger pore sizes was identified to process heavier residues more efficiently. However, since the acidity of ordered mesoporous materials does so far not substantially exceed that of amorphous aluminumsilicates, the high expectations could not be met. If one asks critically, where the advantages of ordered mesoporous materials over more conventional supports lie, enthusiams will most probably be dampened. For catalysis, one of the major points is the high surface area of MCM-41, FSM-16, SBA-15 and all related materials, which can be exploited for depositing metals, incorporating metals in the walls, or grafting species to the walls. However, this high surface area is achieved on the expense of a relatively high susceptibility to hydrothermal degradation and a rather expensive synthesis. Silicas with approximately half the surface area of ordered mesoporous silica are accessible by much cheaper and simpler routes. This is not quite the same for non-siliceous compositions, but here no major efforts seem to have been directed towards their investigation in catalytic applications, yet. A second beneficial feature of ordered mesoporous oxides in catalysis could be the sharp pore size distribution which is reminiscent of zeolites and thus suggests applications in shape selective reactions. However, the pore sizes realized in ordered mesoporous materials are so big, that simple molecules will not be processed shape selectively. Large molecules, on the other hand, are typically so flexible, that the discrimination between differently sized molecules will not be as effective as, for instance, for differently substituted benzene derivatives in zeolites. Therefore, only few publications have appeared, where a clear advantage of ordered mesoporous materials in catalytic applications has been demonstrated which would justify their more expensive and complicated synthesis. In addition, often a good benchmark, such as a high surface area precipitated silica was lacking for comparison, so that the relevance of published data are difficult to judge. Therefore only three examples for the use of surfactant templated mesoporous oxides in catalytic applications shall be highlighted here. More encompassing reviews on their catalytic properties can be found in two review articles [31,32] The first study elegantly used the combination of a suitable acid site strength and the influence of the regular mesopore system for the preparation of acetals from aldehydes [33]. MCM-41 was found to be superior to zeolites and amorphous
aluminumsilicates, if bulky reagents exceeding the size of the zeolite pores shall be converted. The regular mesopore size of the MCM-41 type materials allows the whole pore system to be used even with bulky reagents or products, while zeolitic pores and part of the smaller pores of the amorphous aluminumsilicate are inaccessible and the catalysts are thus less active. It can be envisaged, t h a t other reactions in fine chemistry would benefit from the use of ordered mesoporous materials as well. However, in fine chemistry catalysts are often not tuned to the process, but rather a standard catalyst off the shelf is used. Ordered mesoporous silicas and substituted silicas will have to compete with such s t a n d a r d catalysts. The second example where ordered mesoporous materials were clearly superior to conventional catalysts is a very old process, the oxidation of sulfur dioxide [34]. Nowadays, part of the sulfuric acid is 10( ....... 4--. produced from the sulfur dioxide 90 / "'.~quilibriumconversion released during roasting of sulfidic E 8o V4-111 MCM-41""" ores. Since the smelters tend to use = 70 /SyFeS:l 0 oxygen instead of air in modern "~ 60 ~ . ."" processes, the resulting gas is very ~ 50 ~ "~'. sulfur rich and can not be processed u~ 40 over the conventional vanadium c7 3o v 16os based catalysts. Iron oxide on r 20 surfactant templated silica was found lO to be a suitable, stable catalyst for o . . . . . . . . this reaction and clearly 6oo 700 8oo 9oo looo Temperature [K] advantageous compared to a commercial iron-on-silica catalyst, Fig. 7:SO2 conversion vs. temperature Fig. 7. Also iron oxide deposited on a over v a n a d i u m reference catalyst (V4conventional silica was substantially 111), Fe/MCM-41, and commercial iron less active. The process is ready for catalyst (V1605), from ref [34]. commercialization and a commercial plant would probably use a catalyst based on an adapted mesoporous silica. In the last example the mesostructure has been used essentially as a support for the iron, which is the active component. Another quite spectacular example was published recently, where a single site polyolefin catalyst was anchored in the pore system of ordered mesoporous fibers, and the pore system itself was used as a "nanoextruder" [35]. The resulting polymer consists of crystalline fibers with a diameter of 30 to 50 n m and a very high molecular weight of 6.200.000 Dalton. However, since the real structure of the fibers is circular (see above) the nanoextrusion process claimed is difficult to envisage. The results of the authors are indeed very remarkable, but they seem to have not been confirmed so far. Outside of catalysis, other application fields seem to be quite promising. Feng et al. [36] modified the internal surface of MCM-41 with mercaptopropyl groups. The resulting materials had excellent binding behavior for heavy metals which was far superior to commercial adsorbents [37]. Such modified mesoporous silicas could find applications for water remediation. 9e
Still relatively unexplored, but potentially a large application field of ordered mesoporous materials is optics and electronics. Marlow et al. succeeded in the synthesis of ordered mesoporous silica fibers doped with a rhodamin laser dye [38]. Upon laser irradiation the waveguide effect reported earlier [27] led to amplification by stimulated emission along the fiber axis. The light emitted from the ends of the fibers was spectrally narrowed and highly directional. The effect observed can be described as a mirrorless lasing which can be useful in the construction of optical circuits. A first step in this direction was taken by Yang et al. who produced a prototype optical circuit with waveguides and mirrorless lasers by soft lithography [39]. The decisive step to realize the waveguide on a support was the use of an ordered mesoporous silica thin film. For waveguiding to occur, the waveguide needs to have a higher refractive index t h a n the surrounding. This is a problem, if the silica waveguide is placed on glass or even on silicon, because there the refractive index of the support is similar or even higher t h a n t h a t of the mesostructure. However, a mesoporous silica has, due to the high porosity, a very low refractive index of only 1.15. This allowed confinement of the light in the structure placed on this support and enabled the construction of the optical circuit board. The low refractive index also corresponds to another highly attractive feature of ordered mesoporous materials, i.e. a low dielectric constant. The search for low k dielectrics is very intense in m a n y laboratories in the world, since the semiconductor industry is targeting for dielectric films with k substantially below 2.5. First reports on the dielectric constant of ordered mesoporous silica films by Zhao et al. [40] gave values between 1.45 and 2.1, depending on the exact nature of the film. In a subsequent more extensive study these data were essentially confirmed [41]. Recently the group of Brinker has introduced several highly innovative methods for structuring mesoporous silica thin films, for instance by incorporating a photoacid generator which upon UV-exposure leads to generation of the acid which catalyzes silica condensation. Thus, using masks during UV exposure, thin films of mesoporous silica can be patterned [42]. Also "printing" techniques have been developed by this group to prepare micropatterned structures of ordered mesoporous silica [43]. Due to the easy processability and the variety of different pathways available to prepare [44] and structure films of ordered mesoporous silica, the optical and dielectric properties could indeed lead to their use in technical devices in the electronics industry. 6. P R O S P E C T S
A predicition of future developments is very difficult in any field, but especially so in a fast moving field such as ordered mesoporous materials. Such prospects can only be of a very general nature, partly due to the fact t h a t for any specific interesting idea we would be already working on the realization! The work published so f a r - and one should realize t h a t ten years ago this field of research did not even exist! - suggests, t h a t there are virtually no limitations with respect to the structures and compositions, which can be synthesized as
10 more or less mesostructured compounds. With respect to the compositions, the successful synthesis of metals and mesostructured carbon by the "nanocasting" process suggests a very general pathway to produce ordered mesoporous materials. One will certainly try to load the mesoporous silica templates with various other precursors and then remove the silica structure. If the material which shall be casted is not stable against the conditions used for silica removal (HF or NaOH), one could go one step further and first cast a carbon structure from a silica mold and then, after silica removal, use the carbon negative as a new mold to cast the desired material. The carbon structure can then be removed, for instance, by calcination. It is no great risk to predict exciting developments in this area. With respect to applications, there will certainly be more and more investigations where ordered mesoporous materials are used as catalysts or catalyst supports. However, the more skeptical note of the section on catalysis shall be repeated here: In many cases, much cheaper and simpler alternatives exist, and the properties of ordered mesoporous materials are not so much superior to justify the higher effort of their synthesis. On a longer time scale, non-siliceous compositions will probably be used more frequently in catalysis. If one analyzes the catalytic processes implemented today, the majority is not based on silica as catalyst or support, and the single most important area of aluminumsilicates, acid catalysis by zeolites, seems to be less attractive for ordered mesoporous aluminumsilicates, unless a crystallization of the walls to zeolitic structures or the assembly of such materials from colloidal zeolites to enhance the acid strenght becomes possible. Good opportunities, however, lie in applications outside of catalysis. There are already very promising initial results, such as the adsorbents for heavy metals or the low dielectric constant applications. The big advantage for applications in optics and electronics is the high compatibility of ordered mesoporous silica with the existing technology, since the chemistry is almost perfectly adapted for use with silicon, which is covered by a thin silica layer anyway. Also the methods available for processing, such as spin-coating or dip-coating are well established techniques, and thus relatively small adaption problems are foreseen, although they should certainly not be underestimated. First commercial applications will possibly emerge rather in these fields than in catalysis, but many factors influence decisions to go commercial with a product, so that the future will show, whether and where ordered mesoporous solids will find their first practical uses. 7. A C K N O W L E D G E M E N T S
Research of my group in this field was continuously supported by the FCI and grants from the EU and the DFG which are gratefully acknowledged.
11 8. R E F E R E N C E S
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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
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Clinoptilolite-heulandite: applications and basic research Thomas Armbruster Laboratorium fur chemische und mineralogische Kristallographie, Universitat Bern, Freiestr. 3, CH-3012 Bern, Switzerland Structural peculiarities of clinoptilolite and heulandite are reviewed. Special attention is given to partial Si, A1 ordering within the tetrahedral framework structure. There is strong evidence that the Si, A1 ordering pattern depends on the size, charge, and placing of the original extraframework cations. Even if exchanged to homoionic forms clinoptilolite and heulandite may display different properties depending on the degree and type of Si, A1 ordering. In some cation-exchanged heulandites symmetry lowering from the topological symmetry C2/m to Cm or C1 has been observed due to partial Si, A1 ordering and low symmetry site preference of extraframework cations. Major applications of clinoptilolite are reviewed. In the field of pollution abatement not only the natural product but also surface modified clinoptilolites gain importance. 1. INTRODUCTION Clinoptilolite with the simplified formula (Na,K)6Si30A16072 "nH20 is the most common natural zeolite found mainly in sedimentary rocks of volcanic origin. Such deposits aroused strong commercial interest because clinoptilolite tuffs are often rather pure and can be mined with simple techniques. Approximately 25 years ago ca. 300,000 tons of zeolitic tuff were mined per year [1]. In 1997 ca. 3.6 Mio tons of natural zeolites (mainly clinoptilolite and chabazite) were worldwide produced [2], ca. 2/3 alone were stoped in China. Demand for natural zeolites has increased rapidly over the past decade, particularly in agricultural applications. Growth rates as high as 10% per year are forecasted [2]. A typical zeolite mining company in the USA, Canada, and Europe has less than 50 employees and produces in open pits 20,000 to 50,000 tons per year. Characteristic clinoptilolite rocks consist of 60-90% clinoptilolite with the remaining being mainly feldspars, clays, glass, and quartz. Depending on quality and specification the prize ranges between 50 and 300 US$ per ton. In North America and Europe a large portion of the production goes into the area of animal hygiene including cat litter and other animal bedding products. The rest is divided among applications in animal feed, fertilizer, environmental absorption, and building materials. Zeolitic building material includes dimension stones, pozzolanic cements and concrete, and lightweight aggregates. Some of the pioneering zeolite research has been carried out on heulandite with the simplified formula Ca4A18Si28072 9nH20 because large crystals of this species are available in limited quantities from cavities and vugs in volcanic rocks, e.g. in the Deccan Trap basalts of Western India [3]. Already in 1934 Tiselius [4] studied the temperature, pressure, and concentration dependence of the anisotropic H20 diffusion in heulandite single-crystals. Other
14 recent pioneering studies like atomic force microscopy (AFM) and application of heulandites as electrodes will be discussed below.
1.1. Mineralogical nomenclature Zeolite minerals species shall not be distinguished solely on the basis of the framework Si/A1 ratio. An exception is made in the case of heulandite and clinoptilolite; heulandite is defined as the zeolite mineral series having the distinctive framework topology of heulandite (HEU) and the ratio Si/A1 < 4.0. Clinoptilolite is defined as the series with the same framework topology and Si/A1 > 4.0. The exception is based on entrenched usage of the names heulandite and clinoptilolite, and their convenience for recognizing an important chemical feature [5]. Note that in older studies thermal stability has been used to distinguish clinoptilolite from heulandite. This is a derivative property as an aid to identification, and it is not appropriate as the basis for definition. Individual species in a zeolite mineral series with varying extraframework cations are named by attaching to the series name a suffix indicating the chemical symbol for the extraframework element that is most abundant in atomic properties, e.g. heulandite-Ca, heulandite-Na, clinoptilolite-K, clinoptilolite-Ca etc. [5]. 2. CRYSTAL STRUCTURE The structural topology of the tetrahedral HEU framework [6] is well understood and possesses C2/m space group symmetry with oblate channels confined by ten-membered (7.5 x 3.1 A) and eight-membered tetrahedral rings (4.6 x 3.6 A) parallel to the c-axis. Additional eight-membered ring channels (4.7 x 2.8/~) running parallel to [100] and [102] cross-link the former channels within (010), giving rise to a two-dimensional channel system parallel to (010) responsible for a layer-like structure (Fig. 1).
Fig. 1. Columnar model of the twodimensional channel arrangement parallel to (010) in HEU frameworks. The dark gray columns parallel to [001] represent eight- and ten-membered ring channels. These channels are cross-linked by the light gray eight-membered ring channels running parallel to [100] and [102].
15 There is still doubt about the true symmetry of clinoptilolite and heulandite. Ventriglia [7] determined heulandite to be piezoelectric but none of the subsequent studies on natural samples could confirm this low symmetry (either space group Cm or C1). The possible reason for acentricity is partial Si, A1 ordering within the various tetrahedral sites which is difficult to resolve by analytical or structural techniques. Thus C2/m is the maximum symmetry which may be lowered to C2, Cm, C1, and C1. In addition, multiple polymorphs, distinguished by different distributions of partially Si, A1 ordered tetrahedra, exist in each space group. In a review of C2/m heulandites and clinoptilolites it was found that: (i) in all cases the tetrahedron T2 had the highest A1 concentration but below 50%, (ii) the tetrahedron with the second richest A1 occupation (below 25% A1) could either be T1, T3, T4, or T5 depending on the sample [8]. In analogy to alkali feldspars it can be postulated that each clinoptilolite or heulandite may be structurally different, even if a constant Si/A1 ratio is maintained. This problem is not only of academic interest but has also strong influence on cation diffusion, cation exchange, gas sorption, and catalytic properties, etc.
2.1. Examples of inconsistent properties Gunter et al. [9] used three different natural HEU samples of the following composition, HI: Ca3.6Ko.8A18.sSi27.4072 926.1 H20, H-II: Ca2.1Mg0.3Na2.sK0.3A18.0Si28.2072 925.5 H20, and HIII: Ca3.7Nal.3K0.1A18.9Si27.1072 921.4 H20 to study Pb 2+ exchange. The crystals were crushed to 100-500 Ixm and stirred for 4 weeks in 2 M solution of NaC1 at 100~ to obtain standard conditions (Na-exchanged varieties). After this time only sample H-III was completely Naexchanged whereas samples H-I and H-II stilled revealed significant concentrations of the original extraframework cations in the core of the crystals. In a second step Na-exchanged crystals were treated in a similar way for 3 weeks in 2 M solution of lead acetate to obtain pbE+-exchanged varieties. However, only sample H-III completely exchanged. In particular, sample H-I with a tetrahedral framework composition almost identical to sample H-In revealed only Pb 2+ exchange in a very narrow seam on the rim and around cracks. The reason for this different exchange behavior was not understood [9]. Tarasevich et al. [10] performed K § and Pb 2§ exchange experiments on Na-exchanged forms of two different natural clinoptilolite samples and noted different selectivity for these samples although the difference in the SIO2/A1203 ratio was insignificant and the cation exchange capacities were virtually the same. It should be noted that the selectivity was only different on a quantitative scale. The characteristic exchange sequence of low-field strength zeolites [11, 12] remained uninfluenced. Tarasevich et al. [10] speculated that some specific features of the clinoptilolite structure are responsible for the difference in selectivity. One of their sample formed in nature as Ca-rich variety whereas the other as clinoptilolite-Na. It was suggested [10] that an originally Ca2§ clinoptilolite crystallizes for effective charge balance with a different Si, A1 distribution compared to a Na+-rich clinoptilolite with similar Si/A1 ratio. Thus even in its Na-exchanged form both clinoptilolites have a 'memory' in the sense that the originally Ca 2+ rich sample has a stronger selectivity for Pb 2+ (of similar charge and size) than the originally Na + rich sample which is more selective for K +. This memory effect is imprinted by the Si, A1 distribution. Additional exchange isotherms Pb 2§ (solution) ~ 2Na + (clinoptilolite) were recorded [13, 14] under comparable conditions as in [10]. However, a maximum exchange level of ca. 80% [13, 14] is in contrast to ca. 95% for two different samples [10]. Such discrepancies in the exchange behavior were discussed by Langella et al. [ 14] concluding that the cation exchange
16 selectivity of clinoptilolite is markedly dependent on its original cationic composition, as not all the cationic sites in the structure can be made available for exchange. The pronounced differences in the exchange isotherms (Fig. 2), reported by various research groups [10, 1316], are mainly due to assumption of different cation exchange capacities (CEC) for clinoptilolite. The CEC values are either experimentally determined by different methods or calculated from the chemical composition of clinoptilolite [13, 17]. In most cases, a so-called Na-exchanged clinoptilolite is not completely Na-exchanged but still preserves additional extraframework cations [13, 16]. Furthermore, surface analytical investigations on cationexchanged heulandite have demonstrated that metal accumulation on the crystal surface due to adsorption of soluble and surface precipitation of insoluble hydrolysis products must be considered [ 18].
2.2. The memory effect in HEU frameworks Support for the hypothesis of imprinted Si, A1 distributions during crystal growth depending on the environment and conditions [10] comes from three different approaches: (i) study of growth texture of natural crystals [19], (ii) structure modeling applying lattice energy minimization techniques to HEU frameworks with Na and Ca as extraframework cations [2023], and (iii) synthesis of HEU frameworks prepared from aluminosilicate gels at 180~ in the presence of alkali hydroxides [24].
1.0 .....__..... ....
0.8
/f
-
. . . . . . . . . .
"='---.---==.----
__ .
""'"
iS
........................
/
..7..I
~ o.6ti;
./" ~
/
/
II/ 0.2 0
0.0
.
0.2
0
0.4
~
0.6
0.8
1.0
Xpb (solution)
Fig. 2. Experimentally determined exchange isotherms for Pb 2§ ---, 2 Na § in different natural clinoptilolites at 20 - 25~ and at 0.1 total solution normality: intermediate and long dashed curves [ 10], dotted curve [13], solid curve [14]. The discrepancies of the curves are explained by differences in CEC, extraframework cation distribution, and partial Si, A1 ordering.
17 Akizuki et al. [19], using optical and X-ray techniques, found within one macroscopic 'single crystal' of heulandite domains of triclinic and monoclinic symmetry. The symmetry is different from growth sector to growth sector. The two-dimensional atomic arrangement exposed on a growth-step surface of a tetrahedral (Si, A1) framework differs on each surface. Depending on whether an extraframework cation is adsorbed on the surface, A13§ (for charge balance) o r Si 4+ will be incorporated into the adjacent tetrahedron. Thus the degree of partial Si, A1 ordering is different from growth sector to growth sector depending on its crystallographic orientation and type of extraframework occupant [19]. In other words, each crystal is composed of various polymorphs intergrown in a twin-like relationship. Channon et al. [20] and Ruiz-Salvador et al. [21-23] calculated the minimum energy Si, A1 arrangement for H20-free clinoptilolite-Na, heulandite-Ca, and solid solution members and determined different A1 site preferences depending on type and placing of extraframework cations. Characteristic of such models is that for each bulk composition there are always several possible extraframework cation distributions leading to different Si, A1 arrangements. Although these calculations were performed for anhydrous species, at least a corresponding difference in A1 preference may be expected during crystal growth in a natural hydrous system. Zhao et al. [24] noticed during HEU framework synthesis that for a given aluminosilicategel composition the Si/A1 ratio in the zeolite framework strongly depended on the applied alkali hydroxide. Na and K produced HEU zeolites with an Si/A1 ratio significantly higher than the one in the starting gel, the opposite was found for Li, whereas clinoptilolite-Rb had a composition close to the gel. These results may be interpreted that depending on the alkali cation, a different crystal growth mechanism operates. Thus during crystallization different growth surfaces are exposed leading to a different distribution of A1 tetrahedra [ 19]. 2.3. Low symmetry HEU frameworks There is also direct experimental evidence for low symmetry HEU frameworks. In a series of exchange experiments (K, NH4, Rb, Cs, Cd, and various alkylammonium ions) using as starting material the same Na-exchanged heulandite from Nasik (India) with the original c o m p o s i t i o n Nao.96Ko.09Ca3.54A18.625i27.51072 9 nH20, different space groups (C2/m, Cm, and C1) were analyzed for the exchanged products [25-28]. The differences in symmetry were also reflected in different patterns of Si, A1 ordering. There are two explanation for this observation: (i) The large single-crystals (up to 0.5 mm in maximum dimension) from Nasik were structurally inhomogeneous [19], (ii) the crystals were all triclinic, space group C1, and the observed space group depended on whether the exchanged cations occupied a position on a special position of local 2/m, or m, or 1 symmetry enhancing the symmetry information of the Si, A1 distribution in the framework. The difference of partial Si, A1 ordering alone (deviating from C2/m symmetry) is not sufficiently pronounced to be resolved from an X-ray single-crystal experiment. Notice that not necessarily the 'true' Si, A1 distribution will be resolved in such a diffraction experiment but only the contribution from the Si, A1 arrangement that is in resonance with the 'signals' from the extraframework occupant. Probably a combination of both inhomogeneity and low symmetry enhancement is the reason for the observation of different space groups. Yang and Armbruster [25] studied the structure of two Cs-exchanged crystals both had C1 symmetry but one crystal displayed a more pronounced Si, A1 ordering pattern than the other one. This example suggests an
18 inhomogeneous starting material [19]. For all hitherto analyzed triclinic HEU frameworks the deviation of the tx and ~ angles from 90 ~ was below 0.5 ~ [19, 25, 28, 29].
2.4. Consequences for further research The above observations and discussions indicate that HEU frameworks behave differently compared to most synthetic zeolites with disordered or partly disordered Si, A1 distribution. Even for a given Si/A1 ratio the exact exchange behavior of a HEU framework can not be predicted based on the existing knowledge. One of the reasons is the low topological symmetry (C2/m) of the HEU framework compared to the cubic frameworks of e.g. LTA or FAU. In low symmetry structures the distribution of Si and A1, or the existence of numerous polymorphs, plays a much more important role than in a high symmetry framework. In summary, we have to accept the conclusion [14] that for any 'sophisticated' practical application of natural clinoptilolites specific studies on representative samples from the deposit that is being examined for its exploitation potential have to be carried out. Even exact knowledge of the exchange behavior of well defined synthetic HEU frameworks [24] would not circumvent this problem. For a natural sample we never know its original formation condition and extraframework composition. It could well be that subsequent penetrating fluids in the deposit altered the original composition. The positive aspect of the structural complexity of HEU frameworks is that it offers the chance to learn more about tailor-made design of synthetic tetrahedral framework structures with only partly ordered Si, A1 distribution. 2.5. The Si, AI distribution in 'activated' clinoptilolite For most catalytic applications 'activated' zeolites are required. There are two standard routes how this activation can be achieved. Fairly well understood is ion-exchange to clinoptilolite-NH4 with subsequent release of H20 and NH3 upon heat treatment above 843 K leading to anhydrous clinoptilolite-H with BrCnsted centers [e.g. 30, 31]. Upon dehydroxylation at higher temperature the concentration of BrCnsted sites (acidic hydroxyl groups) decreases and Lewis sites are formed. Heat treatment of clinoptilolite-NH4 above 673 K leads also to partial dealumination of the framework and migration of A1 to extraframework sites [32, 33]. The second mechanism is based on acid treatment of the 'raw' zeolite [e.g. 34]. It was hitherto believed that the extraframework cations are replaced by H30 + and the tetrahedral framework is altered by loss of A1. According to Sychev et al. [34] 27A1 and 29Si NMR spectra of acid treated clinoptilolite-Na indicated that tetrahedral fragments consisting of SiO4 tetrahedra connected to two A104 tetrahedra are attacked, decreasing (for 2M HC1) the A1 concentration from originally 5.9 to 4.1 pfu. Misaelides et al. [35] leached natural heulandites for 48 h with HC1 solution of varying concentration (0.001 to 2 M) and noticed for samples treated with 1 and 2 M HC1 partial surface amorphization and decreasing A1 concentrations from the interior to the rim. The rim approached characteristics of amorphous silica gel [3537]. Yamamoto et al. [38] imaged by atomic force microscopy the (010) surface of heulandite leached with 0.2 N H2SO4 and found pits caused by layer-to-layer dissolution. Heulandite-Na exposed for 15 weeks at 423 K to 0.5 M REEC13 solution (pH 2.8) led to surface erosion and almost complete extraction of Na also in the center of heulandite crystals [39]. The loss of A1 in the center of the crystals was low. Subsequent X-ray single-crystal structure analysis [39] indicated partial rearrangement of framework A1 to hydrated extraframework A1, where A1
19 preferred octahedral coordination. Thus not only H30 § but also A13§ appeared as extraframework cations. In other words acid leaching of heulandite causes (i) A1 and extraframework cation depletion on the surface leading to an amorphous silica layer and (ii) depletion of extraframework cations in the core of the crystals where the HEU framework is still intact. In extreme cases all extraframework cations are lost and for charge balance two different exchange mechanisms operate: Na8A18Si28072 + 8 H30+ ----~[H30+]8A18Si28072 + 8 Na §
(1)
Na8A18Si28072 + 2 Si 4+ ~ [A13+]2A16Si30072 + 8 Na +
(2)
These data indicate that the structural state of acid leached heulandite or clinoptilolite is only poorly defined. The acidity of the solution, the time and temperature of leaching, crystal size, original crystal structure and composition have a strong influence on the leached structure. Variation of any of these parameters may cause variations in the structural state and in the associated catalytic behavior of the leached material. 3. RECENT P I O N E E R I N G STUDIES 3.1. Atomic force microscopy (AFM) Selective catalytic reactions occur also by molecular recognition on the external surface of zeolite crystals and therefore surface-structural information is vital for understanding catalytic mechanisms [40]. Large natural crystals of heulandite are available from various deposits and for this reason some of the pioneering AFM imaging of zeolite surfaces has been performed on these minerals [41-45]. 'Molecular resolution' was obtained for the heulandite (010) face that is densely packed without giving access to the two-dimensional channel system. This face was selected because it is prominent in natural crystals and (010) is also a perfect cleavage plane. In contrast, the resolution of the (100) surface, characterized by channel mouths of the eight-membered ring channels, was considerably poorer. Channel in- or outlets could not be resolved but appeared as undifferentiated grooves. Yamamoto et al. [45] argued that the lower resolution is caused by the tip-sample interactions on corrugated surfaces due to the channel mouths. In addition, it must be considered that faces like (100) are always decorated by traces of the perfect (010) cleavage and have therefore a rough surface. Corresponding lowresolution results were obtained for channel mouths in natural stilbite and mordenite. However, the ordered pore structure characterized by 12-membered tings could be imaged on the (001) face of a synthetic mordenite after scrapping off amorphous coatings [46]. Crystal growth induced steps (n x 9/~) on the heulandite (010) surface are either one or multiple tetrahedral layers thick [45]. Similar features have previously been observed on (010) cleavage plates [42]. In addition, growth spirals [44] and etch pits [38] on heulandite (010) faces were imaged. Adsorption of pyridine bases is generally applied to test the surface acid properties of zeolites. Adsorbed pyridine base molecules interact with the surface acid site and the strength of the interaction can be monitored by spectroscopic methods. Komiyama et al. [47] obtained in situ molecular AFM images of well ordered arrays of pyridine and I]-picoline on the (010)
20 surfaces of heulandite and stilbite and examined their orientation by semi-empirical molecular orbital calculations.
3.2. Clinoptilolite- heulandite electrodes for analytical application A carbon paste electrode modified with Cu2+-doped clinoptilolite powder has been evaluated as an amperometric sensor for non-electroactive NH4 + in flow injection analyses [48]. The conductivity of heulandite single crystals parallel to [ 100] has been studied under isothermal conditions as a function of the H20 content, small polar organic molecule concentration, and charge compensating cations. Results indicate that heulandite electrodes will be applicable for analytical purposes in aqueous solution [49]. 4. APPLICATION
4.1. Ion exchange and adsorption Clinoptilolite and heulandite are low field strength zeolites for which the cation specivities Cs + > R b + >NH4 + > K + > N a + > L i + >I-V, andBa 2+ > S r 2+ > C a 2+ > M g 2+ are predicted[ll, 12]. Corresponding theoretical estimates yielded Ba 2+ > Pb 2+ > Cd 2+ > Zn 2+ > Cu 2+ [16] but experiments revealed Pb 2+ -~ Ba 2+ >> Cu 2+ , Zn 2+ , Cd 2+ . Using clinoptilolite-Na as reference N H 4 + > P b 2+ > Na + > C d 2+ > C u 2 + _= Z n 2+ [ 14] and P b 2+ > N H 4 + > C u 2+ ___-C d 2+ > Z n 2+ ~ C o 2+ > Ni 2+ > Hg 2+ [15] has been determined. Charge-balancing cations present on the surface of very fine-grained clinoptilolite can be replaced by high-molecular-weight quaternary amines [50], such as hexadecyltrimethylammonium (HDTMA) whereas the intemal zeolite cavities remain accessible for small cations. Surfactant modified zeolites (SMZ) absorb CrO42-, benzene, and perchloroethylene (PCE) suggesting that a stable HDTMA bilayer (Fig. 3) formed on the external surface of the zeolite. Nonpolar organic solutes are sorbed by the organic phase whereas anions (CrO42) are retained on the outward pointing positively charged headgroups of the surfactant bilayer [50]. Various types of surfactants on clinoptilolite were applied to extract benzene, toluene, and xylenes from petrochemical spills [51]. HDTMA modified clinoptilolite exhibits enhanced sorption of U 6+ [52, 53].
Fig. 3. Sketchy drawing of HDTMA forming a bilayer (tail to tail) on the surface of clinoptilolite [50]. Nonpolar organic molecules (PCE) partition into the bilayer, anions (CrO42) exchange with the counterions of the suffactant, cations (Pb 2+) bind to the zeolite surface.
21 ~i-MnO2 precipitated on the clinoptilolite surface was successfully applied for removal of Mn 3§ from surface and deep-well water [54, 55] and for the treatment of paint-shop effluents [56].
4.1.1. Pollution abatement Pilot studies of NH4+ removal from municipal wastewater by using clinoptilolite-containing tuff were reported from various countries. After exchange and subsequent regeneration of the zeolite with NaC1/KC1 solutions ammonia was stripped from the solution and an ammoniumphosphate fertilizer was produced. The Tahoe-Truckee Sanitation Agency, California, treated between 1978 and 1993 8.107 m 3 wastewater applying a clinoptilolite tuff for ammonia exchange. The system was designed to accommodate a flow rate of 26,100 m3/day of wastewater and to extract 19.5 mg NH4/liter (507 kg) from a feedwater containing ca 25 mg/liter [57]. Ca-saturated clinoptilolite is used for ammonia removal from NASA's advanced life support wastewater system [58] to establish long term human presence in space. Natural zeolites are also produced for Pb 2§ and Cd 2§ removal from wastewater [e.g. 59, 60] and many other environmental application [61 ]. Low-cost surfactant-modified zeolites (SMZ) have been prepared in multi-ton quantities for use as subsurface permeable barriers to ground-water contaminant migration [50]. Most other studies on SMZ comprise small-scale laboratory experiments [e.g. 62, 63]. 4.1.2. The 1986 Chernobyl disaster In the USA and Great Britain phillipsite-, clinoptilolite-, and chabazite-rich tufts are routinely applied for the decontamination of radioactive wastewater to remove Cs and Sr radioisotopes [e.g. 64]. However, these are small-scale operations compared to the extensive use of natural zeolites at Chernobyl. During the Chernobyl disaster thirty to forty times the radioactivity of the atomic bombs dropped on Hiroshima and Nagasaki were released. The main radioactive isotopes from the Chernobyl accident were ~37Cs, 134Cs, 9~ and 89Sr. The details of zeolite applications at Chernobyl remain rather obscure because of a secrecy problem still remaining after disintegration of the former Soviet Union. About 500,000 tons of zeolite rocks, mainly containing clinoptilolite, were processed at various deposits in Ukraine, Georgia, and Russia specifically for use at Chernobyl [65]. The majority of the zeolites was used for the construction of protective barriers and for agricultural applications in polluted areas. Decontamination of potable water of the Dnieper fiver by using a combination of dust-like clinoptilolite and aluminum sulfate followed by filtration through clinoptilolite layers led to a drastic decrease of radioactivity [66, 67]. In addition, filters of clinoptilolite tufts were suggested to extract radionucleides from the drainage water of the encapsulated Chernobyl nuclear power plant. Filtration reduced 137Cs by 95% and 90Sr by 50-60%. After one year the filters carrying a radioactivity of 10.5 Ci/kg were exchanged and buffed [66]. To reduce Cs radionucleides in cow milk in Bulgaria 10% clinoptilolite was added to the cow feed resulting in 30% Cs reduction in the milk [68]. For Cs decontamination of children chocolate and biscuits were prepared containing 2-30 wt.% pure and powdery clinoptilolite [68]. In Western Europe clinoptilolite was tested to reduce radionucleide levels in soil [69], plants [70], sheep [71], broiler chicken [72], and fruit juice [73]. 4.1.3. Agronomic and horticultural applications The purpose of zeolite application in this field is slow-release fertilization or a combination of ion-exchange and mineral dissolution reactions. Mainly K- or NH4-saturated clinoptilolites
22 are used [74]. The term zeoponics can be applied to the cultivation of plants in any artificial soil in which zeolite minerals constitute an important component, e.g. in microgravity environments or lunar outposts [75]. The first zeoponic space vegetables grown from seeds were tiny radish roots produced on MIR OS in 1990 [76].
4.1.4. Animal hygiene and bedding products Application of clinoptilolite in this area is favorable because of its high NI-I4+ exchange capacity and surface absorption of odors (e.g. ethylene, aldehydes, mercaptans, ketones, H2S). Cat litter is sold in small bags yielding a profitable prize of ca. 800 US$ per ton [77]. Clinoptilolite occupies only a small niche in this market. The majority of cat litter is produced from clays. The annual volume of cat litter worldwide consumed equals about the annual production of natural zeolites. 4.1.5. Nutrition and health The physiological effects of clinoptilolite appear to be related to their high cation-exchange capacity, which affects tissue uptake and utilization of NH4+, Pb 2+, Cd 2+, Cu 2+, Cs +, and other cations in animals [78]. Clinoptilolite appears to be stable in the gastrointestinal tract and reduces ammonia toxicity in pigs and sheep. In ruminants clinoptilolite alters rumen fermentation, thereby modifying volatile fatty acid production by rumen microbes and changing milk and body fat content. Pigs, chickens, and turkeys are protected from mycotoxins in contaminated grains. The aflatoxin concentration in milk is reduced if cows are fed aflatoxin-contaminated feeds. The details of this protection mechanism is not yet understood but adsorption on the zeolite-surface may play an important role. In general, addition of 1 to 5 wt.% clinoptilolite to the diet of animals has been shown to improve growth and feed utilization and to reduce the incidence and severity of diarrhea in pigs, cattle, sheep, and chickens. Ag-exchanged clinoptilolite eliminates the microorganisms E. coli and S. faecalis from water after 2 h of contact time [79]. Clinoptilolite application is not restricted to animals but an anti-diarrheic drug (ENTEREX) has also been developed for humans [80]. Preliminary studies have been performed to test the potential use of clinoptilolite as a matrix for slow drug release [81, 82]. 4.1.6. Gas separation The gas adsorption characteristic of clinoptilolite strongly depends on the extraframework cations [83]. Nitrogen uptake, relative to methane, increases significantly away from the either pure Ca- or K-exchanged form. It is suggested that a specific K-Ca distribution within the structural channels may act as hydration controlled nano-valve [84] permitting diffusion of N2 but repelling CH4. Partly exchanged clinoptilolites applied for N2 and 02 separation from air yielded increasing separation rates for the sequence K > Rb > Na > Cs > Li [85]. There are several patents describing separation of CI-I4 from N2, hydrocarbons from CO2 and N2, 02 enrichment in air, and SO2 separation from air. 4.2. Catalysis As examples, xylene isomerization, toluene hydrodemethylation, n-butene isomerization, dehydration of methanol to demethyl ether, hydration of acetylene to acetaldehyde [31], catalytic reduction of NO [86] have been described to be successful if applying different varieties of treated clinoptilolite (cation exchanged or 'activated'). For a rough estimate about the importance of clinoptilolite for catalytic applications a search in the Chemical Abstracts
23 was performed (clinoptilolite and catalysis) leading to 413 hits between 1966 and 1999 (1-32 papers per year). Due to the low number of publications per year the histogram (Fig. 4) reveals a fairly coarse structure but a maximum in the early eighties and a minimum in the early nineties with a subsequent increase to recent times is recognized. If the statistical clinoptilolite data are normalized to the total number of papers dealing with zeolite and catalysis (31,034 hits) the maximum in the early eighties (ca. 3 % of the papers on zeolite catalysis) becomes even more prominent (Fig. 4). A closer look at research subjects in the statistical peak area does not indicate any specific invention that could be responsible for the increased scientific activity at this time. However, during increased activity (early eighties) more than 70% of the listed papers were written in Russian. In contrast, in 1998 ca. 60% were written in English (20% in Russian) but ca. 40% of the research institutions still belonged to countries of the former Soviet Union. The shallow minimum in the early nineties is characterized by a decreased publication activity in the former Soviet Union. Thus the statistical pattern is governed by the political development in Eastern Europe. During the cold war East European countries had no excess to the major producers of synthetic zeolites thus they developed technologies to use their abundant natural deposits for catalytic applications. The disintegration of the Soviet Union, accompanied by a political and economic crisis, led to a decrease of research activity in this field. The slight recovery of this trend in recent time is associated with an increased number of English papers written by East Europeans (lift of the iron curtain). One may extrapolate that in the future natural zeolites will become less important for catalytic applications.
Fig. 4. Histogram of papers listed in the Chemical Abstracts dealing with clinoptilolite and catalysis. The inlet displays a histogram of papers on zeolite and catalysis. This histogram is used to normalize the clinoptilolite and catalysis histogram. Notice the maximum in the early eighties caused by an increased research activity in the former Soviet Union.
24 5. OUTLOOK The highest profits for clinoptilolite seem to be achieved in the field of cat litter, animal bedding, and odor absorbents. With increasing environmental conscious applications in pollution abatement gain importance, in particular, if large amounts of ion exchanger or absorber are needed. The versatility of surface modified clinoptilolite is not fully explored yet. As the recent example of U 6§ sorption [52,53] on the surfactant indicates, many other applications seem possible where the advantages of the porous bulk structure are combined with specific properties of well-chosen surfactants. Most of the basic research work concentrated on ion exchange behavior studied in form of exchange isotherms. Nevertheless kinetic aspects are equally important [9, 87, 88] and there is a lack of knowledge, in particular for structurally and chemically well-defined clinoptilolites. Structure modeling has to be expanded to hydrous systems [89] to provide better understanding of H20 interactions with extraframework cations and the inner cavity or channel surface. HEU frameworks are interesting research subjects because of the only partly ordered Si, A1 distribution, the low symmetry of the framework, and the different types of channel systems. In this respect understanding of structure and properties of clinoptilolite provides a key for zeolites in general.
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25 18. J. Orechovska, P. Misaelides, A. Godelitsas, P. Rajec, H. Klewe-Nebenius, F. Noli and E. Pavlidou, J. Radioanal. Nuc. Chem., 241 (1999) 519. 19. M. Akizuki, Y. Kudoh and S. Nakamura, Can. Miner., 37 (1999) 1307. 20. Y.M. Channon, C.R.A. Catlow, R.A. Jackson and S.L. Owens, Microporous and Mesoporous Mater., 24 (1998) 153. 21. A.R. Ruiz-Salvador, D.W. Lewis, J. Rubayo-Soneira, G. Rodriguez-Fuentes, L.R. Sierra and C.R.A. Catlow, J. Phys. Chem. B, 102, No. 43 (1998) 8417. 22. A.R. Ruiz-Salvador, A. G6mez, D.W. Lewis, G. Rodriguez-Fuentes and L. Montero, Phys. Chem. Chem. Phys., 1 (1999) 1679. 23. A.R. Ruiz-Salvador, A. G6mez, D.W. Lewis, C.R.A. Catlow, L.M. Rodriguez-Albelo, L. Montero and G. Rodriguez-Fuentes, Phys. Chem. Chem. Phys., 2 (2000) 1803. 24. D. Zhao, K. Cleare, C. Oliver, C. Ingram, D. Cook, R. Szostak and L. Kevan, Microporous Mesoporous Mater., 21 (1998) 371. 25. P. Yang and Th. Armbruster, J. Solid State Chem., 123 (1996) 140. 26. P. Yang and Th. Armbruster, Eur. J. Mineral., 10 (1998) 461. 27. J. Stolz, P. Yang and Th. Armbruster, Microporous and Mesoporous Mater., 37 (2000) 233. 28. J. Stolz, Th. Armbruster and B. Hennessy, Z. Kristallogr., 215 (2000) 278. 29. A. Sani, G. Vezzalini, P. Ciambelli and M.T. Rapacciuolo, Microporous and Mesoporous Mater., 31 (1999) 263. 30. P.A. Jacobs, J.B. Uytterhoeven, H.K. Beyer and A. Kiss, J. Chem. Soc. Faraday I, 75 (1978) 883. 31. D. Kall6, J. Papp and E. Detrektiy, in: D. Kall6 and Kh.M. Minachev (eds.), Catalysis on Zeolites, Akad6miai Kiad6, Budapest, 1988, p. 413. 32. B. Tomazovi6, T. (~erani6 and G. Sijari6, Zeolites, 16 (1996) 301. 33. B. Tomazovi6, T. (~erani6 and G. Sijari6, Zeolites, 16 (1996) 309. 34. M.V. Sychev, V.V. Goncharuk, N.G. Vasil'ev, V.V. Myalkovskii and L.M. Oleinik, Kinetika i Kataliz, 30 (1989) 410. 35. P. Misaelides, A. Godelitsas, F. Link and H. Baumann, Microporous Mater., 6 (1996) 37. 36. K.V. Ragnarsd6ttir, Geochim. Cosmochim. Acta, 57 (1993) 2439. 37. K.V. Ragnarsd6ttir, C.M. Graham and G.C. Allen, Chem. Geol., 131 (1996) 167. 38. S. Yamamoto, S. Sugiyama, O. Matsuoka, K. Kohmura, T. Honda, Y. Banno and H. Nozoye, J. Phys. Chem., 100 (1996) 18474. 39. T. Wrist, J. Stolz and Th. Armbruster, Amer. Miner., 84 (1999) 1126. 40. J.A. Martens, W. Souverijns, W. Verrelst, R. Parton, G.F. Froment and P.A. Jacobs, Angew. Chem., 107 (1995) 2726. 41. A.L. Weisenhorn, J.E. MacDougall, S.A.C. Gould, S.D. Cox, W.S. Wise, J. Massie, P. Maivald, V.B. Elings, G.D. Stucky and P.K. Hansma, Science, 247 (1990) 1330. 42. L. Scandella, N. Kruse and R. Prins, Surface Sci. Lett., 281 (1993) L331. 43. M. Komiyama, T. Shimaguchi, T. Koyama and M. Gu, J. Phys. Chem., 100 (1996) 15198. 44. G. Binder, L. Scandella, A. Schumacher, N. Kruse and R. Prins, Zeolites, 16 (1996) 2. 45. S. Yamamoto, S. Sugiyama, O. Matsuoka, T. Honda, Y. Banno and H. Nozoye, Microporous and Mesoporous Mater., 21 (1998) 1. 46. S. Sugiyama, S. Yamamoto, O. Matsuoka, T. Honda, H. Nozoye, S. Qiu, J. Yu and O. Terasaki, Surface Sci., 377-379 (1997) 140. 47. M. Komiyama, T. Shimaguchi, M. Kobayashi, H.-M. Wu and T. Okada, Surface and Interface Analysis, 27 (1999) 332.
26 48. A. Walcarius, V. Vromman and J. Bessiere, Sensors and Actuators, B56 (1999) 136. 49. O. Sch~if, H. Ghobarkar, A.C. Steinbach and U. Guth, Fresenius J. Anal. Chem., 367 (2000) 388. 50. R.S. Bowman, E.J. Sullivan and Z. Li, in: C. Colella and F.A. Mumpton (eds.), Natural Zeolites '97: Occurrence, Properties, Int. Comm. Natural Zeolites, Naples, 2000, in press. 51. F. Cadena and E. Cazares, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties and Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995, p. 309. 52. J.D. Prikryl and R.T. Pabalan, Mater. Res. Soc. Symp. Proc., 556: Scientific Basis for Nuclear Waste Management XXII, 1999, p. 1035. 53. J.D. Prikryl, F.P. Bertetti and R.T. Pabalan, Mater. Res. Soc. Symp. Proc., 608: Scientific Basis for Nuclear Waste Management XXIII, 2000, p. 281. 54. K. P61yak, J. Hlavay and J. Maixner, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties and Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995, p. 385. 55. V.E. Polyakov, I.G. Polyakova and Yu.I. Tarasevich, Khim. Tekhnol. Vody, 19 (1997) 493. 56. J. Papp, K. Heinzel and S. Adams, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93, Occurrence, Properties and Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995, p. 415. 57. R. Svetich, in: Zeolites '93, Program and Abstracts, 4 th Intemat. Conf. on the Occurrence, Properties, and Utilization of Natural Zeolites, Boise, Idaho, 1993, p. 197. 58. C. Galindo, D.W. Ming, A. Morgan and K. Picketing, in: Zeolite '97, Program and Abstracts, Ischia, Naples, 1997, p. 154. 59. S.L. Peterson, in Zeolite '93, Program and Abstracts, 4 th Intemat. Conf. on the Occurrence, Properties, and Utilization of Natural Zeolites, Boise, Idaho, 1993, p. 153. 60. D. Petruzzelli, M. Pagano, G. Tiravanti and R. Passino, Solvent Extraction and Ion Exchange, 17 (1999) 677. 61. C. Colella, in: NATO Sci. Ser., Ser. E 362, Natural Microporous Materials in Environmental Technology, 1999, p. 207. 62. V.A. Nikashina, P.A. Gembitskii, E.M. Kats and L.F. Boksha, in: G. Kirov, L. Filizova and O. Petrov (eds.), Natural Zeolites - Sofia'95, Pensoft, Sofia, 1997, p. 55. 63. E. Popovici, A. Vatajanu and A. Anastasiu, in: G. Kirov, L. Filizova and O. Petrov (eds.), Natural Zeolites - Sofia'95, Pensoft, Sofia, 1997, p. 61. 64. S.M. Robinson, T.E. Kent and W.D. Arnold, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties and Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995, p. 579. 65. N.F. Chelishchev, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995 p. 525. 66. Yu.I. Tarasevich, J. Water Chem. Technol., 18 (1996) 6. 67. V.T. Ostapenko, Yu.I. Tarasevich, A.E. Kulishenko and T.B. Kravchenko, Khim. Tekhnol. Vody, 22 (2000) 169. 68. L. Filizova, Zeolite'93, Program and Abstracts, 4th Intemat. Conf. on the Occurrence, Properties, and Utilization of Natural Zeolites, Boise, Idaho, 1993, p. 88. 69. M.J. Madruga and A. Cremers, Environ. Impact Radioact. Releases, Proc. Int. Symp. 1995, p. 503. 70. L.S. Campbell and B.E. Davies, Plant Soil, 189 (1997) 65.
27 71. M. Phillippo, S. Gvozdanovic, D. Gvozdanovic, J.K. Chesters, E. Paterson and C.F. Mills, Vet. Rec., 122 (1988) 560. 72. M. P6schl and J. BaltiC, Radiat. Environ. Biophys., 38 (1999) 117. 73. E. Breithaupt, M. Gahlmann, K.D. Buehler and K. Gierschner, Fluess. Obst, 56 (1989) 454. 74. E.R. Allen and D.W. Ming, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, 1995, p. 477. 75. D.W. Ming, D.J. Bata, D.C. Golden, C. Galindo and D.L. Henninger, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, 1995, p. 505. 76. T. Ivanova, I. Stoyanov, G. Stoilov, P. Kostov and S. Sapunova, in: G. Kirov, L. Filizova and O. Petrov (eds.), Natural Zeolites - Sofia '95, Pensoft, Sofia, 1997, p. 3. 77. G.S. Austin and C. Mojtabai, Bull. N. M. Bur. Mines. Miner. Resour.,154 (1995) 267. 78. W.G. Pond, in: D.W. Ming and F.A. Mumpton (eds.), Natural Zeolites '93: Occurrence, Properties, Use, Int. Comm. Natural Zeolites, Brockport, N.Y., 1995, p. 449. 79. M. Rivera-Garza, M.T. Olgufn, I. Garcfa-Sosa, D. Alc~intara and G. Rodrfguez-Fuentes, Microporous and Mesoporous Mater., 39 (2000) 431. 80. G. Rodriguez-Fuentes, M.A. Barrios, A. Iraizoz, I. Perdomo and B. Cedr6, Zeolites, 19 (1997) 441. 81. A. Lam, L.R. Sierra, G. Rojas, A. Rivera, G. Rodriguez-Fuentes and L.A. Montero, Microporous and Mesoporous Mater., 23 (1998) 247. 82. A. Rivera, G. Rodriguez-Fuentes and E. Altshuler, Microporous and Mesoporous Mater., 40 (2000) 173. 83. M.W. Ackley and R.T. Yang, Ind. Eng. Chem. Res., 30 (1991) 2523. 84. D. O'Connor, P. Barnes, D.R. Bates and D.F. Lander, Chem. Comm., (1998) 2527. 85. I.M. Galabova and G.A. Haralampiev, in: The Properties and Applications of Zeolites, Spec. Publ. Chem. Soc. London, 33 (1980) 121. 86. H. Mishima, K. Hashmoto, T. Ono and M. Anpo, Appl. Catal. B: Environmental, 19 (1998) 119. 87. P. Yang, J. Stolz, Th. Armbmster and M.E. Gunter, Amer. Miner., 82 (1997) 517. 88. A. Dyer and K.J. White, Thermochim. Acta, 340-341 (1999) 341. 89. Y.M. Channon, C.R.A. Catlow, A.M. Gorman and R.A. Jackson, J. Phys. Chem., B, 102, No. 21 (1998) 4045.
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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
29
Evolution of extra-large pore materials Mark E. Davis Chemical Engineering, California Institute of Technology, Pasadena, CA 91125
The history of extra-large pore, crystalline materials is briefly reviewed. Relationships between extra-large pore molecular sieves and ordered mesoporous solids are outlined and the difficulties in creating crystalline, mesoporous materials discussed. The possible importance of three-membered rings in the preparation of extra-large pore microporous and/or mesoporous structures is described. The dichotomy between the high cost of production of extra-large pore materials via large, organic structure-directing agents and the low cost of the inorganic solid for typical commercial applications is enumerated and a new synthetic strategy provided to circumvent this problem. Keywords: extra-large pore materials, ordered mesoporous materials, zincosilicates, three-membered rings, large organic structure-directing agents
1.
Introduction
It has been slightly over a decade since the first publication on the existence of an extra-large pore molecular sieve; namely VPI-5 [1]. We suggested at that time the use of the term extra-large pore to describe crystalline materials having pores comprised of greater than 12 tetrahedral atoms (> 12 MR) [2]. This area of scientific endeavor has grown substantially in the past ten years and was certainly one of the factors contributing to the discovery of the ordered, mesoporous materials [3,4]. Here, I will review the brief history of extra-large pore materials, discuss the search for new extra-large pore materials, describe the relationships between extra-large pore materials and ordered, mesoporous materials and end by outlining a new strategy for the preparation of extra-large pore materials.
2.
History of extra-large pore materials
Richard Barrer and his collaborators were the first to publish (in 1969) on the idea of extra-large pore, crystalline materials [5]. Barrer and Villiger presented a series of hypothetical structures related to zeolites L, cancrinite, offretite and gmelinite that had 24 MR pores with free diameters of approximately
30 15 * [5]. Some of these networks consist of known, local atomic arrangements that do not violate crystal chemistry constraints, e.g., bond lengths and angles. The following passage is taken directly from the Barrer and Villiger paper: "Structures of the kind illustrated in Fig. 8 and Table 4, column 5, if they can be synthesized, may be of special significance. Both in respect of accessibility of intracrystalline pores and of total porosity (-- 0.6 of crystal volume) they would be well above any crystal hitherto known." Clearly, Barrer and Villiger set the stage for what was to come. However, what is surprising is that it took over a decade before significant discussions of extra-large pore materials appeared in the literature. In 1984, Smith and Dytrych described nets with channels of unlimited diameter and in particular a series of nets denoted 81 (n) [6]. Nets 81 and 81 (1) later turned out to be the topologies of A1PO4-5 and VPI-5, respectively [1]. Smith and Dytrych realized the significance of this net: "The 81 (n) series of nets is particularly rigid, and might prove useful in engineering design." Additionally, they suggested that large organic species, including chains and helices, should be considered as structure directing agents to prepare extra-large pore materials, e.g., 81(n) where n > 1. It is clear that Smith and Dytrych also anticipated the synthesis of extra-large pore, phosphate-based materials since they discussed the existence of the large channels (15 * ) in the phosphate-based mineral cacoxenite [7]. In the mid-1980's we began a program with the specific goal of synthesizing extra-large pore materials. Using the aforementioned literature as models, we initiated the exploration using large organic structure directing agents (including low generation dendrimers) with both silica and phosphate-based chemistries. In 1986, we prepared the material now denoted as VPI-5. It is not surprising that extra-large pore materials can be phosphate-based because of the existence of cacoxenite. VPI-5 was an unusual extra-large pore molecular sieve since it did not require a large organic structure directing agent for synthesis [8]. After the discovery of VPI-5, numerous phosphate-based, extra-large pore materials were prepared, e.g., see Table 1 of ref. 9, [10], etc. All of these materials require an organic component as part of the synthesis mixture (as does VPI-5 when preparing highly stable, good quality crystals). However, only VPI-5 does not contain organic components filling the pore space in the as-synthesized form. As expected, silica-based extra-large pore materials have also been prepared, i.e., UTD-1 [11] and CIT-5 [12]. UTD-1 requires an organometallic structure directing agent while CIT-5 uses more traditional quaternary ammonium compounds. Thus, the preparations of UTD-1 and CIT-5 follow the reasoning outlined by Smith and Dytrych with regard to the organic phase. The phosphatebased, extra-large pore materials are not consistent with the idea of using large organics since they tend to contain a high volume fraction of smaller organics (that is, they do not structure direct) or none at all (VPI-5).
31 Since the phosphate-based, extra-large pore materials do not reveal stability that is likely sufficient for many commercial applications, I will limit my discussions below to silica-based materials. As I have discussed elsewhere, the lack of stability in phosphate-based materials may not be due to the presence of extra-large rings, but rather to the nature of the structural units [9]. With silicabased, extra-large pore materials, it appears that bulky structure directing agents will be required for their preparation. I will make this assumption in further discussions below.
3. From extra-large pore crystalline materials to ordered, mesoporous materials The announcement of VPI-5 proved that extra-large pore molecular sieves could exist. This report encouraged significant further work. In addition to stimulating research on crystalline materials, VPI-5 played an interesting role in the discovery of the ordered, mesoporous materials. The paper by Kresge et al. in 1992 [3] opened the way for the vast amount of effort that has now been performed on ordered, mesoporous materials. The Kresge et al. report clearly showed the ordering that could occur in these types of materials and some of their properties. They also suggested how these materials may be formed. The solid with hexagonal symmetry was identified early on and several groups suggested that it may be one of the members of the 8 l(n) series for which VPI-5 is 81(1). However, we clearly showed that these types of materials are not crystalline, but more like amorphous oxides since dehydrated samples had Raman bands indicative of planar 3 MR stretching vibrations [ 13]. Crystalline frameworks with 3 MR do not reveal these vibrations [14] as only 3 MR at the surface of amorphous oxides reveal planar 3 MR vibrations [15]. Thus, it was absolutely clear from our results that the ordered, mesoporous materials were not crystalline frameworks [13]. Knowing this, it is expected that the mesoporous materials can be formed from any element combination making amorphous solids (including organic-inorganic materials [16]). Thus, it is not surprising that the ordered, mesoporous materials can be prepared to contain numerous element combinations and ones not available to crystalline solids. Since many properties of crystalline oxides, e.g., acidity, hydrothermal stability, etc., are the essential features exploited in commercial applications of these oxides, it is not unexpected that the ordered, mesoporous materials have not yet found much commerical use. The large void volumes, pore sizes and surface areas of the ordered, mesoporous materials provide advantages over microporous solids in certain areas of application but issues such as stability remain. Thus, if crystalline, extra-large pore solids could be prepared in the pore size and void volume ranges of the mesoporous materials, they would be immediately commercialized. The question remains as to why crystalline materials of this size range have not been synthesized. Navrotsky et al. have shown that pure silica, ordered, mesoporous silicas are energetically very close to pure silica, crystalline
32 molecular sieves [17]. For example, pure silica FAU has an enthalpy of 13.6 + 0.7 kJ/mol relative to quartz while MCM-41 has a value of 14.5 + 0.5 kJ/mol. Since the thermal energy at 373 K is 3.1 kJ/mol, these two structures are well within the available thermal energy of one another. Also, I predicted that if the materials were to be synthesized from aqueous solutions, they would have void fractions of approximately 0.8 or below [9]. There are ordered, mesoporous materials that conform to this limit. Thus, one is left to ponder why crystalline mesoporous materials have not yet been synthesized. The ordered, mesoporous materials can be prepared by many synthetic routes. This is not surprising since the lack of crystallinity does not place as many demands on the assembly process as with zeolites. By following the assembly process with in situ NMR, we were able to show that the high temperature construction of MCM-41 involved the formation of organic aggregates that subsequently ordered silica to form the final composite [18]. At other conditions, the assembly process can be different and involve layered phases [ 19]. Since it is now established that layered materials can be transformed into crystalline solids, e.g., MCM-22 [20], FER [21], VPI-5 [22], ERB-1 [23], the lack of crystalline mesoporous materials is not likely due to the inability to form layered intermediates. A possible reason for the lack of a crystalline mesoporous material could be related to the nature of the building units used for assembly. In 1989, Brunner and Meier [24] published a correlation between the framework density, FD (number of tetrahedral atoms per nm3), and the minimum ring size in the structure (MINR). For structures where the smallest ring for certain T-atoms is variable, the MINR value would have a + associated with it, e.g., MINR = 4+ for structures with some T-atoms in 4 MR whereas for others it is larger. I articulated some of the implications of this correlation at the time of the Brunner-Meier publication [25]. Of importance, I mentioned the possible synthesis of MINR = 3 or 3+ structures using elements other than beryllium because of its toxicity. If the Brunner-Meier correlation is correct, then the highest void volume, crystalline silica likely already exists. Since 3 MR are not synthetically feasible with crystalline silicas, a MINR = 4 framework will contain the highest void volume. From the Brunner-Meier correlation, the FAU topology is near the maximum void volume for MINR = 4 structures. To achieve the higher void volumes like those of the mesoporous materials, MINR = 3 or 3+ structures may need to be prepared. Berylosilicate chemistry does promote the formation of 3 MR as evidenced by a number of berylosilicate minerals, e.g., lovdarite, phenakite, euclase, and a synthetic analogue of lovdarite does exist [26]. However, the use of beryllium renders berylosilicates to be commercially unacceptable because of toxicity issues. Thus, in 1989, we began a program to prepare MINR = 3 or 3+ materials using zincosilicate chemistry since there are many zincosilicate analogues to 3 MR-containing berylosilicates. Listed below are the new zincosilicates prepared in our group.
33
Table 1. New Zincosilicates Material
Structure
Si/Zn
Pore Size
M I N R = 3+
Re f.
VPI-7
VSV (FD= 17.1)
3.5
9 MR
yes
27
VPI-8
VET (FD=19.8)
> 20
12 MR
no
28
VPI-9
VNI (FD= 16.7)
4
8 MR
yes
29
VPI- 10
no code (FD= 15.3)
3.5
9 MR
yes
30
Zn-ANA
ANA (FD= 18.6)
4
8 MR
no
31
Zn-SOD
SOD (FD= 17.2)
6
6 MR
no
32
CIT-2
no code (FD=15.8)
4
9 MR
yes
33
CIT-6
*BEA (FD=15.0)
> 15
12 MR
no
34
Additionally, Rohrig and Gies [35] have synthesized a zincosilicate denoted RUB-17 (RSN, FD = 16.8, MINR = 3+). Zinc is a relatively inexpensive, nontoxic element and as shown above, can be used to prepare MINR = 3+ materials. Additionally, there is a MINR = 3 zincosilicate mineral giving precedence for the existence of MINR = 3 micro and/or mesoporous, crystalline solids. Thus, the use of silica-based frameworks containing zinc could in principle lead to commercially viable extra-large pore materials that may be near the porosity of the ordered, mesoporous materials. A new strategy for synthesizing extra-large pore materials It is clear that crystalline, extra-large pore materials would be of significant commercial interest. The problem is their preparation and ultimately control of their properties. Based on the known extra-large pore materials, silicabased systems would be preferred over phosphate-based ones when dealing with issues such as stability and acidity. Another critical item is cost. For numerous applications, e.g., cracking and other refinery processes, the materials cannot be expensive. If one assumes that large organic moieties will be necessary for the preparation of extra-large pore, silica-based materials, the costs of the organic components are not compatible with the ultimate application of the porous solid. Thus, this issue must also be resolved. In some cases, the organic can be extracted from the molecular sieve. For pure-silica *BEA, Jones et al. [36] were able to extract the tetraethylammonium fluoride that was used as the structure directing agent (SDA). In that case, a small organic was used to prepare a 12 MR material. In some aspects, this situation is 4.
34 like that of the small organics used to prepare some of the extra-large pore, phosphate-base materials. The major difference of course is the stability of the inorganic portion; *BEA has very good stability while the phosphate materials do not. In principle, the small organics could organize and pack into ordered arrangements to yield large void spaces upon their removal. However, in practice, this type of organization has yielded only non-crystalline mesoporous materials (organics can also be extracted from mesoporous materials [13]). Thus, if a single large, bulky organic is necessary to structure direct extra-large pore, crystalline materials and the cost of the final product is somewhat limited, then how does one achieve the goal of producing such a material? In Fig. 1 a schematic of a new concept for the synthesis of extra-large pore materials is shown and illustrates how the previously posed question may be answered. component A + component B
ble
extra-large f pore z ~ l i t e / /
~~~)
+ [component A + component B] extra-large ~ [or precursors to] pore zeolite ~
disassemble ~ component C, ~ e.g., at low pH
~
bulky component C (SDA)
.
ynthesis,
( component )~_...-~
~
e.g., at high pH extra-large pore zeolite
Figure 1. New Concept for Extra-Large Pore Zeolite Synthesis [37] The idea is to combine two or more components into a large, bulky organic structure directing agent. The assembly can be via the formation of covalent bonds and/or through non-covalent interactions. The assembled SDA must remain stable to synthesis conditions, e.g., high pH with zeolites, in order to structure direct an extra-large pore material. Upon formation of the organicinorganic composite, the organic component now is disassembled at conditions that are not sufficient to harm the inorganic structure. The key to this concept is that the organics formed from the disassembly of the SDA can be re-assembled to make again the SDA. Thus, a large, bulky SDA is used to prepare the inorganic
35 structure and the components of the SDA are recycled in order to make the cost of the synthesis low. Numerous strategies can be employed with this idea. The concept is not unlike what happens in the assembly of the ordered, mesoporous phases. However, for the synthesis of extra-large pore crystalline materials, the assembly most likely will involve a small number of molecules (likely 2 or 3) to form the SDA and covalent linkages may also be exploited.
5.
Summary
The areas of extra-large pore, crystalline solids and non-crystalline, ordered mesoporous materials both continue to flourish. By investigating further the fundamental rules involved in their syntheses, it may be possible to make new solids with the advantageous properties of both existing classes of materials. Some of the issues of concern when performing such syntheses have been outlined here and several new suggestions for research provided.
REFERENCES [ 1] M.E. Davis, C. Saldarriaga, C. Montes, J. Garces and C. Crowder, Nature, 331 (1988) 698. [2] M.E. Davis, P.E. Hathaway and C. Montes, Zeolites, 9 (1989) 436. [3] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli and J.S. Beck, Nature, 359 (1992) 710. [4] T. Yanagisawa, T. Shimizu, K. Kuroda and C. Kato, Bull. Chem. Soc. Jpn., 63 (1990) 988. [5] R.M. Barrer and H. Villiger, Z. Kristallogr., 128 (1969) 352. [6] J.V. Smith and W.J. Dytrych, Nature, 309 (1984) 607. [7] P.B. Moore and J. Shen, Nature, 306 (1983) 356. [8] M.E. Davis, C. Montes and J.M. Garces, ACS Syrup. Ser., 398 (1989) 291. [9] M.E. Davis, Chem. Eur. J., 3 (1997) 1745. [10] G.Y. Yang and S.C. Sevov, J. Am. Chem. Soc., 121 (1999) 8389. [11 ] C.C. Freyhardt, M. Tsapatsis, R.F. Lobo, K.J. Balkus Jr. and M.E. Davis, Nature, 381 (1996) 295. [12] M. Yoshikawa, P. Wagner, M. Lovallo, K. Tsuji, T. Takewaki, C.Y. Chen, L.W. Beck, C. Jones, M. Tsapatsis, S.I. Zones and M.E. Davis, J. Phys. Chem. B, 102 (1998) 7139. [13] C.Y. Chen, H.X. Li and M. E. Davis, Microporous Mater., 2 (1993) 17. [14] M.J. Annen and M. E. Davis, Microporous Mater., 1 (1993) 57. [15] C.J. Brinker, R.J. Kirkpatrick, D.R. Tallant, B.C. Bunker and B. Montez, J. Non-Cryst. Solids, 99 (1988) 418. [16] S. Inagaki, S. Guan, Y. Fukushima, T. Ohsuna and O. Terasaki, J. Am. Chem. Soc., 121 (1999) 9611. [17] A. Navrotsky, I. Petrovic, Y. Hu, C.Y. Chen and M.E. Davis, Microporous Mater., 4 (1995) 95.
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C.Y. Chen, S.L. Burkett, H.X. Li and M.E. Davis, Microporous Mater., 2 (1993) 27. A. Firouzi, D. Kumar, L.M. Bull, T. Besier, P. Sieger, Q. Huo, S.A. Walker, J.A. Zasadzinski, C. Glinka, J. Nicol, D. Margolese, G.D. Stuckey and B.F. Chmelka, Science, 267 (1995) 1138. M.E. Leonowicz, J.A. Lawton, S.K. Lawton and M.K. Rubin, Science, 264 (1994) 1910. L. Schreyeck, P. Caullet, J.C. Mougenel, J.C. Guth and B. Marler, J. Chem. Soc. Chem. Commun., (1995) 2187. M.E. Davis, C. Montes, P.E. Hathaway and J. M. Garces, Stud. Sur. Sci. Catal., 49 (1989) 199. R. Millini, G. Perego, W.D. Parker Jr., G. Bellussi and L. Carlussio, Microporous Mater, 4 (1995) 221. G.O. Brunner and W.M. Meier, Nature, 337 (1989) 146. M.E. Davis, Nature, 337 (1989) 117. S. Ueda, M. Koizumi, Ch. Baerlocher, L.B. McCusker and W.M. Meier, 7th IZC, Tokyo, Poster Paper 3C-3 (1986). M. Annen, M.E. Davis, J.B. Higgins and J.L. Schlenker, J. Chem. Soc. Chem. Commun. , (1991) 1175. C.C. Freyhardt, R.F. Lobo, S. Khodabandeh, J.E. Lewis Jr., M. Tsapatsis, M. Yoshikawa, M. Camblor, M. Pan, M.H. Helmkamp, S.I. Zones and M.E. Davis, J. Am. Chem. Soc., 118 (1996) 7299. L.B. McCusker, R.W. Grosse-Kunstleve, Ch. Baerlocher, M. Yoshikawa and M.E. Davis, Microporous Mater., 6 (1996) 295. R.W. Grosse-Kunstleve, Ph.D. Thesis, Swiss Federal Institute of Technology, ZUrich (1996). M. Annen, Ph.D. Thesis, Virginia Polytechnic Institute, Blacksburg, VA (1992). M.A. Camblor, R.F. Lobo, H. Koller and M.E. Davis, Chem. Mater. 6 (1994) 2193. P. Wagner, unpublished. T. Takewaki, L.W. Beck and M.E. Davis, J. Phys. Chem. B., 103 (1999) 2674. C. Rohrig and H. Gies, Angew. Chem. Int. Ed. Engl., 34 (1995) 63. C.W. Jones, K. Tsuji and M.E. Davis, Nature, 393 (1998) 52. M.E. Davis and S.I. Zones, U.S. Pat. Appl. (2000).
Studies in SurfaceScienceand Catalysis135 A. Galarneau,F. Di Renzo,F. Fajulaand J. Vedrine(Editors) 9 2001 ElsevierScienceB.V.All rightsreserved.
37
E v o l u t i o n o f R e f i n i n g and P e t r o c h e m i c a l s . W h a t is the place o f zeolites Christian Marcilly Institut Franqais du P6trole, Division Cin6tique et Catalyse, 1 et 4 Avenue de Bois Pr6au, 92852 Rueil Malmaison, France.
Introduction Refining and petrochemicals are the industries where zeolites are by far the most frequently used for adsorption and catalysis. The earliest application goes back to the end of the fifties, after the discovery by the company Linde of the synthesis of the A-type zeolite (1) capable of separating normal and branched paraffins. The second, and certainly the most significant event was the introduction of X and Y-type zeolites in catalytic cracking at the beginning of the sixties, which generated some deep technological changes in the process and substantial gains in gasoline yield. The first use of shape selectivity properties for zeolites dates back to 1968 with selective hydrocracking on erionite for normal paraffins of gasoline cuts. Over the last 40 years, zeolites were introduced first in refining, and then in petrochemicals, and now hold what may be considered a key position. The future of zeolites in refining and petrochemicals is obviously for a large part, directly related to the evolution of these two sectors, and we will be looking at their development in the first part of this paper. In the second part, we will discuss the place occupied by zeolites among catalysts and adsorbents used in refining and petrochemicals, and will briefly discuss some possible potential application for the future.
1. REFINING AND PETROCHEMICALS: EVOLUTION AND CHALLENGES IN THE 21st CENTURY Obviously it is not possible to discuss the long term prospects of these two domains of the petroleum sector seriously without referring to that of the petroleum resources that supply them.
1.1. The future of petroleum resources At the end of 99, world proven reserves were estimated at some 145 Gigatons (Gt) (2). These proven reserves will be depleted in about 40 years at the present rate of consumption (3.4 Gt/year) (2) and in 29 years if the growth in world consumption is 2 % a year. The ultimate reserves are extremely difficult to assess, as there are many unknowns. The figures given, which depend on the nature of the reserves considered and the degree of specialists' optimism, vary considerably. For instance, the liquid hydrocarbon reserves (conventional and non-conventional crude and gas-associated liquids) are estimated at 370 Gt i.e. 2,700 Gb by the IEA (International Energy Agency) and at 645 Gt i.e. 4,700 Gb by the DOE/EIA (Energy Informatibn Agency) (3). Depending on which hypothesis is adopted at the outset, the world production in liquid hydrocarbons is expected to reach a maximum in about 2015-2035. Depending on the growth
38 scenarios, ultimate reserves of 370 Gt should cover 60 to 100 years requirements (4, 5) and those of 645 Gt over 150 years. So the liquid hydrocarbon reserves are still substantial but their mobilization will demand significant efforts of research to make them usable (2). Sometime in the middle of the 21 st century, we will be turning to natural gas as the principal source of energy, coal and new renewable energies should remain at a modest level (6). Although the present petroleum resources are quite sufficient to satisfy the requirements of the first half of the 21 st century, their many and varied locations do pose a problem. The major part (66.5 %) of the 145 Gt of proven petroleum reserves is to be found in a geographical zone (The Middle East) where the political climate is unsettled, and on which the world will be depending more and more in the coming decades. Moreover, most consumer zones are far from producing zones, which means a intensive transportation activity between the two.
1.2. The demand in refined and petrochemical products 1.2.1. The development of requirements from 1970 to the end of the 2 0 th century Over the last thirty years, refining and petrochemicals have known an unsettled time with two oil crises (causing an economic downturn on a world wide scale), the Gulf war and an awakening of awareness regarding the degradation of our environment. Table 1 (2, 7) shows the development of the world petroleum consumption structure between 1970 and 2000. The following landmarks stand out : 9 The heavy fuels sector dropped rapidly, from 30 % in 1970 to 13 % in 2000 (a sharp and massive drop in the demand of electric power stations). This decrease should continue but at a slower rate. 9 By contrast, the part of light products increased during this period; especially that of middle distillates (jet fuels and gas oils) which increased from 27 to about 35 % between 1970 and 2000 and is likely to continue to grow, mainly due to the increased number of diesel engines among the European automotive population, whereas the proportion of gasoline has remained fairly steady since 1970. Table 1" Evolution of the structure of the demand in petroleum throughout the world (market economy countries) between 1970 and 2000. 1970 1980 1990 2000 106 t o n s % 106 t o n s % 106 t o n s * % 106 t o n s % Gasolines 492 25.4 626 26.6 750 26.8 876 26.2 Middle distill. 530 27.4 721 30.6 950 33.9 1163 34.8 Heavy fuels 608 31.4 645 27.4 500 17.9 426 12.8 Others 307 15.8 363 15.4 600 21.4 875 26.2 Total 1937 100 2355 100 2800 100 3340 100 Middle distillates: jet fuels, heating oil, diesel-oil. Others: refinery gas, LPGs, naphtas, solvents, lubricants, wax, bitumen, petroleum coke ... * Approximate values At the end of 1999, the world refining capacities were a little below 4.1Gt, with a low growth rate of about 10 % over 10 years (3.74 Gt in 1989).
39 In petrochemicals, the demand in olefins stagnated between 1978 and 1982 and then picked up and has grown fairly steadily since then, a little over 5 % a year on average, increasing from 65 Mt to126 Mt approximately between 1983 and 1997 (8). This annual growth can be broken down as 5.3 % for ethylene, 6 % for propylene, 15 % for isobutene and 2.2 % for butadiene (9). At the same time aromatics were on the increase, with an average growth of slightly under 5 % between 1983 and 1997, increasing from 30 Mt to some 57 Mt (8). During this period, benzene and especially PX, had the strongest growth, especially in South-East Asia. In 1997, world production of benzene represented a little less than half of the production of monoaromatics (27 Mt) (10). In the past 30 years, in order to handle changes in both the quantity and quality of demand, European refining has become more complex (table 2 ), stepping up conversion capacity (FCC in particular) and installing new hydrotreatment (reduction of sulphur content in fuels), hydrocracking and gasoline production units (11). The trend is even more strongly marked in the Asia-Pacific region due to the fast development of certain countries in the zone (South Korea for instance). Figures were noticeably high in 1999 compared with 1989, and this was also due in large part to the fact that China has recently been taken into account (China has over one third of the FCC units in the Asia-Pacific region). In North America, hydrogenating processes (HDT and hydrocracking (HDC)) continue to progress, whereas the others (cracking and special processes) appear to be stagnating. On a global scale, world refining capacities showed a downturn in the eighties due to the petroleum crises of 1970 and the resulting economic slump. Refining capacities picked up again in the nineties under the stimulus of the reduction in the price of gasoline and the economic expansion of South-East Asia, among other things. Table 2 (12-16): Development in the structure of world refining capacities between 1979 and 1999 and for the main geographical zones in Mt/year (the zones that did not have a market economy in 1979 and 1989 are not included in these two periods but are integrated in 99 : Former Soviet Union, China, North Korea, several Eastern European countries etc.). N. Amer. 437 260 46 997
1979 W. Asia World N. Eur. Pacific Amer. 346 214 9 523 49 30 400 304 6 1 9 72 998 520 3210 870
1989 W. Asia World N. Eur. Pacific Amer. 311 240 1290 577 88 51 531 298 15 14 130 84 832 500 2840 923
1999 W. Asia Eur. Pacific 404 374 106 125 34 35 723 982
HDT FCC. HDC Atm. Dist. HDT : Hydrotreatments, FCC : Fluid catalytic cracking, HDC : Hydrocracking, Atm. crude in atmospheric distillation.
World 1835 688 201 4077 Dist.:
1.2.2. Development forecast in market demand for products in the year 2010. Without any major changes in the general trend of demand, the policies applied regarding energy and crude prices should mean that annual petroleum consumption will increase from 3.3-3.4 Gt/year to over 5 Gt/year in 2020. In the coming decades, refining and petrochemicals will probably be operating in a restrictive context marked, among other things, by the following political-economic requirements :
40 9 The Environment : more respect for the environment will be demanded, limiting the release of pollutant gases (NOx, SO• volatile organic compounds), or discharge of contaminating liquids and solids, as much as possible. 9 Consumption : master consumption of petroleum products in order to limit gases with greenhouse effect (CO2 in particular), which will also help to preserve non-renewable resources. 9 Growth : promote the development of developing and newly developed countries as much as possible, controlling pollution and consumption. Maintain minimum sustainable growth making it possible to absorb the technological mutations imposed by progress (policy of full employment). 1.2.2.1. Quantitative demand It is interesting to assess what world refining will look like in the year 2010, considering both a developed geographical zone and one being developed. Table 3 (2) shows the development between 1990 and 2000 and that forecast between 2000 and 2010 in the demand for various petroleum products (especially gasoline, middle distillates and heavy fuels) in Europe (East + West), in the Asia-Pacific region (excluding Japan) and world wide. The global consumption of petroleum products increases only very moderately in Europe (the same applies to the United States) but more significantly on a global scale due to the substantial contribution of developing countries, in particular Asia. As shown on Table 3, the least developed part of the Asia-Pacific region has caught up with Europe by 2000 and will be well ahead of it in 2010. The forecast for 2010 for global demand in petroleum products reaches the 1999 figure for global refining capacity (4.1 Gt approx.) which should therefore increase moderately in the coming years. Table 3: Expected development of the demand for various petroleum products in Mt/year, in the European Union (EU), Asia-Pacific and the world between 1990 and 2010) (2) Europe* Asia-Pacific ** World Years 1990 2000 2010 1990 2000 2010 1990 2000 2010 Gasoline 138 153 168 114 183 253 746 876 1047 Middle distill. 235 303 342 174 312 451 950 1163 1472 Heavy fuels 90 77 60 82 104 132 504 426 456 Others 134 183 207 93 227 291 600 875 1046 Total 597 716 961 463 826 1127 2800 3340 4021 * Western + Eastern Europe (countries of former Soviet Union excluded) (Eastern Europe 10-15 % of Western Europe) ** Asia-Pacific except Japan Others: refinery gas, LPGs, naphthas, solvents, lubricants, wax, bitumen, petroleum coke ... Regarding petrochemicals, the demand in olefins and aromatics is, and will remain steady. Between 1995 and 2005 the demand for olefins is expected to grow at a rate of over 4 % on average, and that for aromatics by 3.6 % (8). Among the olefins, demand will typically be in the region of 4 to 5% for ethylene, 5 to 6 % for propylene, 6 % for isobutene and 3.3 % for butadiene (9, 17).
41 Forecasts up to 2003-2005 for the global demand in aromatics shows a growth of all monoaromatics, but it will vary considerably according to the compound considered and according to information source (10): it is in the range of 3.5 to 4.5 % a year for benzene (10, 17), from 5 to 8 % for PX approximately and significantly lower for the other aromatics (2, 10). What stands out, is the lack of balance between the growth in demand for benzene and xylene. The overall demand for petrochemicals should reach about 250 Mt in 2005 (8).
1.2.2.2. Changes in product quality Specifications regarding product quality have been getting increasingly stringent since the seventies, and this trend is most probably going to continue during the coming decade. The known or estimated development of specifications for the principal petroleum products between 1996 and 2010 is shown in Table 4 (2). Table 4: Evolution of specifications for three major petroleum products between 1996 and 2005 - 2010 (2) Europe Specifications Gasoline S (ppm) Benzene (% vol.) Arom. (% vol.) Olefins (% vol.) Oxygen (% vol.) RON/MON Diesel fuel Density max. S (ppm) Cetane number Cetane index Dist. 95% vol. Polyarom. (% mass) Total Aromatics Domestic fuel S (% masse) Heavy FO S (% masse)
Average Califomia (4)
1996-99
2000
2005 (project) ....
2010 (z) (possibility)
500 5
150 1 42 18 2.7 95/85
50 <1 ? 35 14 h 18 ? < 2.7 ? 95/85 ?
< 10 _<1 _<35 < 10 < 2.7 95/85 ?
18-20 0.4-0.6 23 3.5-4.0 2.0-2.2
0,860 500 49 46 370
0,845 350 51 46 360 11
0,840 h 0,845 ? 50 51 ~ 53 ? 48 h 50 ? 340 b. 360 ? 3 ~ 11 ?
0.82-0,84 _< 10 > 55 > 52 < 340 <2 < 15
0.842 140 53.8 ? ? ?
0,2
0,2
0,2
0,1 (3)
2
2
1 (l)
2.7
(l) probable maximum value for 2003. (2) extreme values considered for fuels by automobile manufacturers (World-wide fuel charter, April 2000). (3) specification coming into force in 2008 but already taken into consideration in the choice of new HDS units to be built for 2005. (4) ref. 18.
42 The gasoline pool is obtained by blending gasolines from various origins (Table 5): Straight run, Reforming, FCC, coking, hydrocracking, isomerization, alkylation, polymerization and additives (butane, ethers). Table 5 gives the average percentages of these various components in a gasoline pool for the United States in the nineties (2, 19-24) and in a western European pool and indicates the main characteristics of each. Table 5: Components of the gasoline pool: typical contents and characteristics Source
U S A % W.Eur. S(ppm) Arom. Benz. Olef. RON MON RVP (19-24) % (2) vol% vol% vol% (kPa) Distill. 3.8 7.5 100-200 2-4 1-2 < 1 65-80 60-75 70-80 Reform. 34.0 40 0 60-75 3-5 < 1 100 89 30-35 FCC 36.0 27 500-2000 25-35 0.7-1.5 40-50 93 80 40-50 Pyrolyse - 0 - 0 2. ~ 4.103 5-60 2-35" 20-35 82-96 74-85 70-80 Hydrocr 2 - 0 0 2-5 3 < 0.5 85 80 70-80 Isom. 4.5 10 0 < 0.5 < 0.5 < 0.5 85-88 82-85 70-80 Alkyl. 13 9 0 < 0.5 <0.5 < 1 94 92 40-45 Polym. - 0 -~ 0 0-150 < 0.5 < 0.5 > 95 95 82 60-70 Butanes 5 5.5 0 0 0 95 92 ** MTBE 1.7 1.0 0 0 0 113-117 95-101 55 * benzene -- low values in the case of low T pyrolysis (VB or Coking) and very high in the case of Steam cracking. ** 1% nC4 --)+ 50 kPa
Most of these gasoline sources present various problems regarding changes in specifications: 9 Gasolines from steam cracking have a high content of S, benzene and other aromatics. 9 FCC gasoline has a high content of S and olefins, with a somewhat poor octane number (MON for example). 9 Reforming gasoline is highly aromatic. The increased hydrogen production sought for the refinery will lead to an increase in the content of aromatic compounds, for which an outlet has to be found in petrochemicals. In all cases, the benzene content must be lowered 9 Hydrocracking gasoline has inadequate octane. Rich in naphthenic structures, it provides an excellent reforming feed, but in this case adds to the production of aromatics which are likely to be excessive for the market. The diesel fuel pool is also a mixture of basic products from various different origins (Table 6) (2, 21):
43 Table 6: Components of the diesel pool" typical contents and characteristics (2, 21) Source W. Eur% GO Str. run 70-90 * GO pyrolysis <5* LCO FCC < 10 * GO HDC < 10 * GO Oligom. - 0 Fischer-Tropsch 0 *" after suitable HDT of sulphur-rich
S (ppm) Arom. (vol%) 3 &20.103 20-40 > 20.103 30 ~ 60 14.103 60-85 < 20 8 < 1 0 < 1 0 diesel fuels
Cetane 42-54 28 ~ 45 18-27 > 60 < 50 > 75
Cloud Point -10 &+5 -4 ~ - 8 -10 < - 15 < -48 -9
The sources of gas oil that raise problems are, in order of importance : 9 FCC gas oil (LCO (Light Cycle Oil)) : it has a high S content and low cetane number and may be hydrotreated after blending (-~ 30 % for example) with straight run gas oil, but it is difficult to improve the cetane of the LCO (+ 6 to 15 points only depending on conditions) (20,25); 9 steam cracking diesel fuels 9 these have a very high content of aromatics especially dealkylated polyaromatics. The typical aromatics content of most diesel fuels is more in the 30-35 % range, and although there are no particular specifications for the total aromatics content, this content is bound to drop due to the foreseeable evolution of S and specific gravity specifications which will limit integration of LCOs and pyrolysis gas oils in the gas oil pool (26). Pollutant emissions from automobile vehicles, whether running on gasoline or diesel fuel, do not depend much on the composition of the corresponding fuels. However, for new models of both categories of vehicle, the reduction of pollutant emissions will need technologies (lean bum engine, NOx traps, etc) which demand fuels with a very low sulphur content. Therefore, it is to be expected that the specifications will become even more stringent in the coming years meaning further constraints for refiners in forming the fuel pools (2). As regards petrochemicals, the general quality-related trend of the main products researched, olefins and aromatics, tends towards greater purity.
1.3. Changes in refining schemes (27) Present tendencies and those in the coming decades regarding changes in refining requirements for catalyst processes, operate within a context marked by 4 key constraints : 9 The almost total disappearance in the demand for heavy fuel oil with a high sulphur content (except for maritime heavy fuels) and the loss of the corresponding outlets for heavy residues. 9 The need to have clean processes producing clean products to reduce polluting gaseous, liquid and solid discharge.
44 An active concern about the risk of global warming (problem of. CO2). The maintenance of a policy for cutting costs at all levels in order to adapt to a constantly changing technical-economic world, and survive. This being so, refining processes will be called on to evolve. As there are many processes, we will only be looking at them briefly and classifying them in three major categories: processes : those that reduce the molecular weight of the feed (conversion), those that mostly modify the structure of the molecules without changing their size, while eliminating certain impurities (improved quality), and finally those that increase the average molecular weight of the feed (synthesis). 1.3.1. Conversion 1.3.1.1. Standard conversion The two major processes concerned here are catalytic cracking and hydrocracking which convert vacuum distillate type feeds (cracking can also absorb part of the atmospheric residue (AR)). In spite of the average or even inferior quality of the gasoline that it produces and the poor quality of some of its by-products (LCO and residue), catalytic cracking is an unavoidable and economic conversion tool in refining and its capacity on a world-wide scale is going to continue to grow. 1.3.1.2. Deep conversion The drop in demand for heavy fuel oil which is expected to continue in the coming years and the continuous growth in the demand for white (light) products, should promote the increase in capacities for the conversion of residues and more specifically vacuum resid (VR). However, due to the high investment costs required, the present low yield of this conversion, and the existence of alternative solutions (exporting of residues, sourcing with lighter crudes with a low sulphur content, reorganising existing units etc.), refiners have adopted a "wait and see" attitude and will continue to do so for the next few years. This development of refining should be looked at as a medium, or rather a long term (5 to 15 years) solution. So catalytic conversion tools can be expected to take the lion's share, thermal processes (coking and thermal cracking) which are much less selective being kept for highly contaminated residues (28). The hydrotreatments required for deep conversion demand additional hydrogen to make up that supplied traditionally by the refinery reformer. The new source of hydrogen may by supplied by a gas steam-reforming unit, but more often by partial oxidation of the ultimate residue as it makes it possible to totally convert the residue into synthesis gas. 1.3.2. Petroleum cut quality improvement Between 1990 and 1999, the global capacity of hydrotreatment had already increased by more than 40 % and is expected to continue to grow in the coming years. Certain cuts that escaped hydrodesulphurization in the past will have to undergo this treatment in the future (certain kerosenes and straight run gas oils or FCC gasolines).
45 In order to satisfy the octane requirements for gasoline, C5-C6 isomerization units will become more common, whereas reforming will continue to grow but a little more slowly. Today, reforming is unavoidable as a provider of hydrogen and a high octane number gasoline, and the very low pressure operation also allows significant progress for these two objectives but produces more aromatics. The latter should be introduced in limited quantities in gasoline, and petrochemicals should absorb at least part of the excess production. Concerning the improved quality of gas oils and lube oils, of which a steadily increasing proportion will be provided by hydrocracking, it will be necessary to build units for the controlled hydroisomerization of long paraffins contained in these cuts in order to improve the cold resistance while minimizing losses through cracking.
1.3.3. Synthesis processes The processes concerned are more particularly : aliphatic alkylation, olefin oligomerizations and etherifications (28). The gasoline obtained by isobutane-olefins alkylation is an ideal component for the gasoline pool through its substantial contribution to the octane number and the absence of aromatics and olefins. The technologies used go back a long way and are technically well mastered, but the liquid catalysts used pose some problems : human risk regarding hydrofluoric acid, large quantities of waste ("red oils") that have to be retreated for the sulphuric acid. These problems somewhat slow down development which would otherwise be rapid. Oligomerizations make it possible to produce high octane number gasolines, but their strong olefinicity demands saturation by hydrogen. These processes will probably only have a limited growth in the future. The production of gas oil by oligomerization will remain marginal as the cetanes obtained barely exceed a value of 50. Etherifications are proven processes which do not raise any specific problems and should spread rapidly unless the banishing of ethers from gasolines decided in California spreads to the rest of the United States and then the world. 1.3.4. Refining scenarios for 2010 Figure 1 (29) shows a typical refining scheme for 2010 and the rest of the decade. Every refinery would not be able to house all the installations presented, as the corresponding investments would be too heavy. However, overall, the refineries in the same oil corporation should correspond more or less to this scenario. It includes deep conversion units with a POX for residues for refinery hydrogen production, hydrotreatments on all the distillation cuts and the LCO of the catalytic cracker and specific additional units for quality improvement : isomerization of light paraffins, aliphatic alkylation and etherification.
46 Figure 1 : Refining scenario for 2010 (29)
1.4. New deals for refining and heavy petrochemicals 1.4.1. For the refiner 1.4.1.1. Refining, hydrogen and self-consumption The expected evolution for refining (deeper hydrodesulphuration, better product quality and finally, in the long run, deep conversion) means a significant growth in the hydrogen requirements of the refinery (28, 29). Compared with the simple refinery (hydroskimming) of the seventies and eighties, the hydrogen demand of the whole refinery in 2010 and the decade shown in Figure 1 could be multiplied by a factor in the order of 5. The production of hydrogen would be one of the principal reasons for the increase in selfconsumption. This increase would be very limited to start with in classic refineries that will gradually be acquiring the equipment to comply with the new specifications imposed, without going so far as to install a resid hydroconversion or a POX unit. It is thus expected that the increase will only be from 6 to 7 % of the crude treated in the European Union between 1996 and 2010 thanks to the savings made at the same time by the refiners (11), especially through the use of co-generation on a much larger scale. But as shown on Table 7 (2), it could become significant for a complete refinery corresponding to the scenario on Figure 1.
47 Table 7: Evolution of investments, self-consumption and of the hydrogen demand for an average refinery Type of refinery
Investments (G$)
Self-consumption (% wt of crude) - 4 -6 -~ 10
H2 consumption (3)
Simple 0.5 tx Classical conversion 1 - 1.5 (l) 2 c t - 3tx Deep conversion (2) 2.5 5c~ (~): according to product quality (2): including specific units devoted to improving quality (3): the figures given are not absolute, as the hydrogen consumption, and therefore of tx, will depend on operating conditions (nature of the treated crude, S content of the products, etc.) The production of hydrogen by steam-reforming of methane or by partial oxidation of heavy residues (POX) inevitably leads to an increase in self-consumption and additional emissions of CO2.
1.4.1.2. Refining and sulphur Gaseous sulphur emissions coming from the refineries and their products, represent a risk for the environment (smoke and acid rain) and a health hazard. Also gas emissions containing sulphur from the combustion of fossil fuels inhibit the catalysts of exhaust systems and there is every reason to think that the level of 50 ppm fixed for 2005 for gasoline and gas oil may well only be a step towards levels closer to zero (2, 30). Regulations regarding the sulphur contents of petroleum products and sulphur emissions from the refinery, mean that most of the sulphur is now recovered in Claus and Claus tail gas units in the refinery in the form of elemental sulphur. Figure 2 shows the changes between 1996 and 2005 in the distribution of sulphur leaving an average sized refinery treating 8.1 Mt/year of a crude with 1.13 % S (i.e. 91,506 t of S). Part of the sulphur leaving the refinery is distributed among the products and gaseous emissions of the refinery, the rest is collected in the form of elemental sulphur. Between 1996 and 2005, the part of the sulphur in the gaseous emissions drops significantly, but it is mainly that present in the refining products that is reduced (from 51 to 37 %), leading to a substantial increase in elemental sulphur production (from 41 to 57 %) (31).
48 Figure 2 9 Evolution of the distribution of sulphur leaving a refinery between 1996 and 2005 (31)
Refining is now a major sulphur (S) producer, and will become even more so. For instance, a large refinery, such as that of Shell at Rotterdam which treats some 20 Mt crude a year, already produces between 250,000 and 300,000 tons of S per year (32). The production of S worldwide (inclusive of all forms) in 1998 was about 62 Mt, with 40.5 Mt in the form of elemental sulphur (32) produced mainly by refineries (approximately 1/3) (33) and natural gas. This figure is expected to increase to 68.5 Mt in 2003 and then 74.5 Mt in 2008, with 47.8 and 53.1 Mt respectively of elemental S, the proportion of S recovered from fossil hydrocarbon sources increasing steadily. At the present time the zones with the highest S production (inclusive of all forms) are North America which comes far ahead of Asia and Europe (32). The main outlet for S is sulphuric acid (90 % approx.) with the two main outlets for utilization being fertilizers (approximately 60 % of S) and chemicals (textiles, solvents, paints, detergents etc.) (31, 34). However, certain outlets (SO4H2,CS2) are expected to have a lower demand by the year 2008 (35). For several years, the offer of sulphur has already exceeded the demand, which has led to significant lowering of prices (34, 36, 37). Over about fifteen years, the price of sulphur has therefore dropped from a value of over 100 $/t to much lower values fluctuating between 45 and 65 $/t. The coming decades are likely to be marked by an even greater production excess (32, 36, 37). Initially a valuable industrial product, sulphur has become a by-product, which has already made some traditional production sources unprofitable and forced them to cease activities. It is fast on the way to becoming a waste if new outlets are not discovered (37).
1.4.1.3. Refining and CO2 In addition to the limitation of traditional atmospheric pollutants such as the sulphur and nitrogen oxides and hydrocarbons, we now have to consider the reduction of greenhouse gases, in particular CO2.
49 1.4.1.3.1. CO2 in the atmosphere and the world climate Carbon dioxide is said to be the main culprit in global warming. Although the heating power attributed to it is considerably less than that of other pollutants (about 30 times less than CH4 and 200 times less than N20), the significant CO2 contents in the atmosphere mean that this gas is the principal contributor to the greenhouse effect (about 55 % in 1990) (38). The coinciding of industrial development of human society and the increase in the CO2 content in the atmosphere explains why the latter is considered as being mainly due to human activities. Since 1860, the year in which the second industrial revolution started (the time when electricity and petroleum were discovered), the average concentration in CO2 in the atmosphere has increased from 288 ppm to 315ppm in 1957 and 368 ppm in 2000, meaning an increase of almost 30 % in 140 years (39). Experts predict that this tendency will continue reaching a possible figure of 600 ppm in 2050. The awareness of the risk presented by CO2 for the future of the climate began well before 1990, and in spite of a lack of knowledge and perspective making it difficult to grasp the true validity and full impact, ecologists and many scientists called for preventive measures to be taken urgently (40). The Kyoto Protocol, adopted on 10 November, 1997 within the framework of the master convention of the United Nations on the climate change, and appealing to industrialized countries to reduce their greenhouse gas emissions by an average of 5 % by 2010 compared with 1990, could not be respected, because for one thing the timeline was too short to allow effective technologies to be developed and diffused (41), and for another thing, there is reason to doubt the motivation of a certain number of countries implicated.. However, even although the summit of The Hague in November 2000 did not end in the hoped for decisions being taken, in the coming years, we can expect CO2 emissions to be increasingly taken into account at all levels of human activity. 1.4.1.3.2. The role of human activities in the total CO2 emissions world-wide: Out of the 28 Gt of CO2 released every year into the atmosphere by human activities, some 21.5 do in fact come from fossil fuels and the rest, i.e. 6.5 Gt are due mostly to deforestation (34, 42, 43). The figure of 28 Gt does indeed appear low compared with the 770 Gt/year of natural CO2 emissions (i.e. 96.5 % of the total emissions) (43), and from this view point industrial activities (industries, electric power stations) and those related to transport would only be responsible for 2.2 % of global emissions and petroleum only for 1.3 % (44, 45). But unlike natural emissions which are part of a natural carbon cycle and are offset over one year by the same volume of CO2 that is absorbed or transformed, these 28 Gt would be considered as an excess volume of emissions, not offset in the yearly cycle (this still has to be ascertained). It is generally accepted that a minimum of 120 years would be necessary to return to the initial situation of 1860 if CO2 were to be brought back to its level at that time (39). Table 8 (43) which shows the emissions of CO2 world wide according to type of human activity, shows that transport is responsible for a little less than 20 % of these emissions. But emissions due to transport are essentially a phenomenon of developed countries. For instance in the United States, transport contributes 32 % of CO2 emissions, three quarters being due to road transport (46).
50 Table 8" Annual emissions of CO2 due to human activities (1996) (*) Activity
% of 28 Gt % of total emissions , (800Gt) Electric power stations 25 0.875 Residential and tertiary 23 0.805 Industry 19 0.665 Transport 18 0.63 Private vehicles 5,5 0.19 Trucks 6 0.21 Planes 3 0.1 Ships 1,5 0.05 Other 2 0.07 Burnin/~ of the biomass 15 0.525 (*): These CO2 emissions differ significantly from one geographical region to another.
1.4.1.3.3. Refining and CO2 : need to adopt a rational approach (47-49) The impact of measures taken regarding CO2 should not only be considered in terms of emissions from motors but must be the result of an overall assessment from the time the crude enters the refinery up to the end use of finished products. Such an assessment would inevitably point to the necessity to find compromises : 9 A first and short term compromise should be found between the reduction of the sulphur and the increase in refinery self consumption. Low sulphur content fuels, the production of which is responsible for an increase in CO2 emissions, is only necessary for vehicles fitted with new technologies. Is it really necessary to supply an automobile population with these fuels as early as 2005 when the major part of the population will not yet be fitted with the new technologies? (50) 9 A second compromise between the other specifications which will be set for fuels in 2005 and the increase in self-consumption has also to be found. Some of these specifications are effectively interdependent and this interdependence must be taken into account when selecting them. For instance, in the future why would it be necessary to keep the aromatics content below 35% in gasoline if the almost complete elimination of sulphur enables total elimination of harmful hydrocarbons discharged in exhaust gas (50)7 A similar question can be asked regarding the lowering of the T95 in diesel fuel which aims at limiting the formations of polyaromatics and soot in exhaust gas, when eventually diesel vehicles will be fitted with particle filters (50).
51 Balancing the production of finished refinery products is also a kind of compromise and a less well known way of minimizing CO2 emissions : the example given below shows that adopting a position outside the large domain of acceptable variations for ratios between the production of gasoline and gas oil, has a negative impact on energy consumption and therefore on refinery CO2 emissions. Actually, these emissions, although significantly lower than those of vehicles running on gasoline and diesel fuel (approximately 7 to 8 times less) (47) are far from negligible. Extreme operating limits of a refinery, the principal conversion tool of which is the FCC, correspond to middle distillates/light distillates (light distillates - gasolines) (MD/LD) ratio which are roughly equal to 1 and 2. Between these two values, the refinery modifies the gas oil/gasoline ratio of its fuel production by playing on the nature of the crude supply and the cut points of the products, but globally, CO2 emissions remain more or less constant. The MD/LD ratio equal to 2 corresponds to a proportion of diesel engines of the automobile population of about 25 %. At the present time, a country such as France has already, in the year 2000, a 33 % proportion of diesel engines (MD/LD ratio of 2.3 approx.) and should reach 37 % in about 2005. By contrast, the American situation corresponds to an unbalanced market in the other direction, with an MD/LD ratio that is well below 1 (about 0.6). It is therefore interesting to find out what happens to the CO2 emissions on either side of the previous operating range. Figure 3 (48) shows that any significant imbalance between the gas oil and gasoline productions lying either on the "all gas oil" side or on the "all gasoline" side of the "optimum equilibrium" range generates a rapid increase in the emissions of CO2 emissions in the refinery. If France had to produce its own diesel gas oil, it would have to carry out some large scale installation work in hydrocracking units, or even hydroconversion of residues, which would lead to a sharp increase in global CO2 emissions. Other European countries also encourage the sale of cars running on diesel fuel, and from this point of view, a country such as Spain is at present European leader with 49% licensing of new public vehicles running on diesel against 39 for France and 25 for the European average. By contrast, excess emission of CO2 corresponding to the American situation is due mainly to the need to produce gasoline by a deeper conversion of the crude (including by hydrocracking of the FCC LCO) which means an increase in refinery self-consumption. At the present time, excess emission of CO2 is partially avoided in France, through an intense import-export activity. In order to ensure a balance between offer and demand, France imports gas oil and exports its excess gasoline, but manages to generate less pollution than the United States where the opposite is the case. This situation is obviously precarious and can be disrupted by any change in the energy policy of one of the actors. The most rational approach would therefore consist in reducing the rate of the production of diesel engines in France and in Spain and increasing that in the United States.
52
Figure 3" Impact of a change in the ratio between middle distillates and light distillates on refinery self-consumption (middle distillates = jet fuel + diesel oil +FOD; light distillates = gasolines). (48) Refinery self-consumption (or C O 2 emissions)
(a.u.)
"*.,_
USA I l +
:: : : I .... I 0 0.65 Gasoline max
S )ain
:: Optimum : equilibrium zone : I 1
/
Prance I
Europe J a p a n (EU)
i : : I 2
: l
, i i
i
i
i i 2.35 2.5
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1.4.1.4. A stronger interaction between refining and petrochemicals in the future (5 l) Faced with the complexity of the demands and increasingly stringent constraints, the two industries, refining and petrochemicals, will gradually have to tighten the bonds which had become somewhat slack over the last two decades. They will have to strengthen their exchange of products and make the most of all opportunities of complementarity in order to adapt to the new economic context. The following points can be given as examples : 9 Evolution of steam cracking feeds. Less availability of light naphthas, more and more frequently used by refining for reformulated gasoline, will oblige petrochemicals to look towards lighter feeds (petroleum gas, C3-C4 cuts from refineries with the olefins eliminated as well as gas condensates which could become significant feeds in the future) or towards heavier petroleum cuts with higher aromatic contents. 9 Recovery of light olefins for the petrochemical industry from a certain number of refinery effluents : refinery ethylene gas, propylene from the FCC LPGs 9 Recovery of effluents rich in hydrogen for the refinery and of isobutene and isopentenes from the steam-cracking C4 and C5 cuts respectively, for the production of ethers if these are not prohibited in gasolines. 9 Recovery of aromatics extracted from gasolines. By the year 2005, there will be a surplus of aromatics on the European market. The problem is that the European and world markets for aromatics are small compared with the corresponding gasoline markets. (Figure 4 ) (18). Thus the 1998 European market of aromatics is 13 Mt which breaks down into 6.5 Mt of B, 2 of T, 2.5 of X (mixture) and 2 of isomers (OX+PX) (18). The 1998 European market (East + West) for gasoline was about 168 Mt and the world market of 975 Mt (2). Every % of benzene in world gasoline represents about 1.5 times the European benzene production i.e. -~ 9.7 Mr. It should be possible for the European petrochemical sector to
53 absorb the surplus of benzene and of the other aromatics created by the enforcement of the 2000 specifications ( 1 % and 42 % in gasoline respectively) (18). This sector at present produces some 13-14 Mt of aromatics. However the limit of 35 % for aromatics in gasoline expected for 2005 will probably mean a further excess of over 10 Mt on the market if all the aromatics were to be extracted. (18) Such a quantity of aromatics could not be absorbed by the market and would cause prices to collapse (18). In such a situation, only the refineries that are large enough with a good enough performance could allow themselves to produce low cost aromatics. The others would have to find other solutions. 9 Use by the refining sector of processes initially developed by petrochemicals such as steam-reforming of natural gas, partial oxidation of residues, Fischer-Tropsch synthesis etc. Figure 4 (18): 1998 markets of aromatics in Asia, North America and Europe compared with corresponding markets and world markets of gasoline
1.4.2. For catalyst manufacturers and holders of process licenses (2, 52-54) Refining and heavy petrochemical industries can, on average, be considered mature industries (2, 51) where the differences between catalysts and/or the technologies of various competitors decrease. Thus, catalyst manufacturers and license holders attach increasing importance to factors of cost and productivity in order to remain competitive and survive (52,
54 53). In difficult economic context, this leads to turbulent times when associations and company mergers proliferate, all the actors seeking to strengthen their positions regarding innovation, productivity and commercial activities. In the coming decades, for the catalyst manufacturers, and for process license holders, the purpose will be first and foremost to remain competitive regarding the performance of commercialised products and their costs. The need for technical or technological innovation, whether small or big, to improve products or introduce new ones, remains a fundamental requirement, and from this view point, the rapidity at which innovations can be produced becomes of major importance. New method are still appearing (increasingly sophisticated techniques for characterisation, combinatorial chemistry, molecular modelisation, rapid information access and analysis) which will make it possible to speed up the rate at which innovations occur in the near future. But innovation is not the only lever for success. Other levers are in fact increasingly important for keeping ahead of the competition : 9 Cost reduction (improved productivity); 9 Proposal for complete sets of processes and catalyst systems; 9 Improvement of the number and quality of services associated with the catalyst and/or the process (integrated set of services for sale, technical assistance, treatment of used catalysts or recovery of worn catalysts etc.). 2. C A T A L Y S T S IN THE INDUSTRY. IMPLICATIONS
REFINING AND PETROCHEMICALS AND OPPORTUNITIES FOR ZEOLITES
2.1. Catalysts: World market In 1999, the world market for catalysts (including precious metals) reached 9 G$ with 24 % for refining, 23 % polymers, 24 % chemicals and 29 % environment. Table 9 gives the refining catalyst market in tons and $ by application for 1999 and 2005 (2). Table 9 1999 2005 Processes 103 tons % G$) 103 tons % G$) Cracking 495 77 0.7 560 73.6 0.83 Hydrotreatments 100 15.5 0.72 135 17.7 0.96 Hydrocracking 7 1.1 0.10 9 1.2 0.12 Reforming 6 0.9 0.12 7 0.9 0.15 Others - 35 5.5 0.56 -~50" 6.6 0.64 Total solids - 640-650 100 2.2 -760 100 2.7 Alkylation .3100' 0.85 3700* . 1 ~
r catalysts for H2 production, polymerization, isomerization, etherification., Claus, lubes etc... * approximate values. En 1999, North America accounted for about 30 to 40 % of the market in $ depending on the sources of information (2, 55, 56) and Western Europe for 20 %. In 2005, their respective shares will be about 35-38 % and 19 % of this market.
55 Regarding petrochemicals, the world market of catalysts represented 2.16 G$ and 630 Mt in 1999 and will probably account for 2.53 G$ and 735 Mt in 2005 (2). 2.2. Zeolites: applications and general trends of development 2.2.1. Zeolites: main fields of application and markets (2, 57, 58) The world zeolite market has developed strongly over the last decades and at present represents some 1.6 Mt per year (58), with about 290,000 t/year for natural zeolites (approximately l 8 %) used in ionic exchange and adsorption. Applications of synthetic zeolites concern three major fields of activity amounting to some 1.3 Mt : detergents (A-type zeolites), adsorbents and desiccators (A and X-type zeolites mainly) and finally catalysis (especially Y-type zeolite). In 1998, the world market for these synthetic zeolites was approximately 1.6 G$, of which catalysis represented a little over 50 %) (2). As shown on Table 10 which gives these fields of activity according to major geographical regions, the share of catalysis in tons is much less and only represents a little over 12 %:
Table 10: Consumption of synthetic zeolites in thousands of tons (1998)
Detergents Catalysts Adsorb/Desic Total
N. Amer. 275 80 43 398
W. Eur. 505 25 27 557
E. Eur. 55 15"5.5 75.5
Japan Other 85 130 10 30 6.5 18 101.5 178
TOTAL 1050 160 100 1310
The expected evolution over 5 years (up to the year 2003) is on average a moderate global growth in the order of 1 to 1.5 % per year approximately for catalysis, from 1 to 2 % for adsorbents and desiccators and, for detergents, a slight decrease on average (-~1-2 % per year) in the major developed countries (lower quantities of zeolite in detergents). Out of the 1.3 Mt of synthetic zeolites produced annually, the A-type zeolite, with 1.1Mt, is by far the most commonly used (58). Its principal field of application is in the detergent industry, where certain modern detergents contain up to 40 % weight. About 100,000 tons per year of synthetic zeolites go to the adsorption sector (58-60) : desiccation and purifying standard applications (insulating windows mostly, refrigeration, treatment of natural and industrial gas, purification of olefins, desiccation of alcohols) and separations (n-paraffins, xylenes, PSA/VSA systems for the production of oxygen or hydrogen etc.). Among the zeolites used, the A-type zeolite is in a large majority (58) for desiccation and separations in particular, followed by X-type zeolite for the elimination of traces of polar impurities, and to a lesser degree, by various zeolites with high silicon contents such as mordenite and ZSM-5 for desiccation of acid gases or the elimination of volatile organic compounds. Regarding catalysis, almost all the zeolites used in the world are used in refining and petrochemicals. In refining, the principal applications are cracking (FCC), hydrocracking, isomerization of C5-C6 cuts and dewaxing or isodewaxing. In petrochemicals, the principal use is in aromatic transformation (alkylations, isomerization, disproportionation/ transalkylation) which, in 1999 represented 8.4 % and 6 % respectively of the financial volume and tonnage of petrochemical catalysts, i.e about 2 % of the financial volume of
56 world catalysts. The Y-type zeolite present in the FCC catalysts alone accounts for almost 95 % of the world consumption. Speciality zeolites, which account for only a few % of the world consumption of zeolites in catalysis, are mainly Y-type zeolites modified for hydrocracking and ZSM-5 zeolite as FCC additive. The production of other zeolites remains marginal. In all, out of 126 known zeolitic structures, only about a dozen are used in industrial or pre-industrial applications (2, 61, 62); these are the following" 9 A : (detergents, desiccation and separation) ; 9 F A U : X (desiccation, purification, separation) and Y (separation, catalysis) ; 9 M O R : (adsorption and catalysis) ; 9 LTL : KL-type zeolite (catalysis: aromatization) ; 9 MFI : Silicalite and ZSM-5 (adsorption and catalysis) ; 9 B E A : Beta-type zeolite (catalysis: cumene) ; 9 MTW : zeolite MCM-22 (catalysis: ethylbenzene, probably cumene ?) ; 9 CHA 9SAPO-34 (methanol to olefins or MTO process- demonstration unit ); 9 F E R : Ferrierite (skeletal isomerization of n-butenes- demonstration unit) ; 9 AEL and/or TON : SAPO-11 and possibly ZSM-22 (improvement of pour point for petroleum cuts by straight long paraffin isomerization) ; 9 Structures not revealed (for aromatic Cs isomerization) : one is certain (IFP) and the second is possible (UOP). 2.2.2. Openings
f o r z e o l i t e s in r e f i n i n g a n d p e t r o c h e m i c a l s
Zeolites have been present in refining since the beginning of the sixties (FAU cracking) and in petrochemicals of first generation intermediaries since the seventies ( transformation of aromatics on MOR). The success of zeolites in second generation intermediary chemistry and fine chemicals (63-73) are on the whole, more recent (63-70, 72, 73) and benefit from the zeolitic materials developed mostly for the first two industries. Significant improvements of these materials are still possible, and new applications using new materials or not yet used so far, will be emerging in the coming decades. However, it is very likely that from this point of view, fine chemicals will be more profitable than the mature industries like refining and petrochemicals for at least two reasons: (i) the variety of reactions is greater and the catalysts far from optimized (ii) the products have an added value that is greater and may make the high cost of certain zeolitic material acceptable. However, the quantities of products involved in the fine chemicals sector are small, and the volumes of zeolitic materials used will still be minor compared with those of refining. Considering the specifications imposed relating to petroleum products in general and fuels in particular, the refining industry and that of petrochemicals has, and will always have a need for more active catalysts and even more for more selective catalysts. On the latter point, zeolites will continue to hold a strong position to offer innovative solutions. The opportunity concerning the progress that they can provide must be sought first of all in existing processes or new processes aiming at producing the following hydrocarbons : 9 Light olefins from C3 to C5 as raw materials for petrochemicals or for the production of clean, good quality fuels. 9 Highly branched paraffins from C5 to C12 for the gasoline pool or longer and slightly branched paraffins for the kerosene and gas oil pools.
57 Specific molecules as first and/or second generation intermediaries in petrochemicals: alkylmonoaromatics in particular. From this point of view, the development of processes of inter-transformation of these aromatics can certainly be expected. More precisely, the following few opportunities for zeolites can be mentioned : 9 FCC : although it is not likely that the Y-type zeolite will be replaced as principal active agent, there may be room for additives enabling selective production of light olefins ranging from propylene to pentenes as long as these additives are competitive with the ZSM-5 regarding costs, activity and stability. 9 Hydrocracking (HDC) : the main factor for progress here would be to find a zeolitic catalyst dedicated to the production middle distillates, associating both the activity and the stability of zeolites and the selectivity of amorphous catalysts. 9 Aliphatic alkylation : the best zeolite found to date is the Beta-type zeolite, which does not contribute any octane gain compared with existing processes. A three-dimensional zeolite, more open than the Beta and at least as active, would be needed for this application. 9 Isomerization of paraffins : in the domain of middle paraffins from 7 to 9 carbons of the gasoline fraction, there is a need for a catalyst making it possible to achieve a thorough isomerization selectively (2 branches or more) while minimizing the cracking. However this is a difficult challenge for a bifunctional acid catalyst. 9 Dewaxing (gas oils, HDC residues, lube oils) : recent innovations in this domain (dewaxing by hydroisomerization) represent a significant breakthrough compared with classic processes by hydrocracking (on MFI structure). Progress is still possible in particular to further limit loss through cracking of isomerized products at high conversion. 9 Hydrodecyclization of polyaromatics of middle distillate cuts (LCO in particular) remains a significant challenge. The difficulty which acid catalysis comes up against is that the cycle opening is generally slower than the consecutive cracking of open products. 9 Transformation of aromatics : nearly all catalysts used are zeolitic. New zeolites can still provide gains in selectivity and stability. Also, the alkylation of aromatics other than benzene is of interest (ethyltoluene, isopropylbenzene, disopropylbenzene, paraethyltoluene, alkylnaphtalenes et dialkylnaphtalenes etc.). 9 Hydrotreatments : several studies have made it possible to detect some interesting potential among certain metal sulphides dispersed in the zeolites to desulphurize and denitrogenate certain refractory heteroatomic molecules (certain alkyldibenzothiphenes for example). One of the difficulties that has to be solved is to avoid excessive cracking of the hydrocarbons to be purified. 9 In the field of adsorption/separation, significant progress can be expected with the optimization of materials that are already known (crystalline defects, Si/A1 ratios, nature and position of cations, external surface properties, crystal size etc.) and the discovery of new materials.
58 Zeolitic membranes. In spite of many studies carried out since the eighties, the penetration of zeolitic membranes in industry has been very slow and has still not been integrated in refining and petrochemicals activities. These do however, represent an important application potential in the long term in the domain of molecular separation for certain catalytic separations. Considerable progress remains to be made regarding manufacture of these membranes (74).
Conclusion The global demand for petroleum products and therefore the capacities of refining and petrochemicals will continue to grow for many years to come. Refining and petrochemicals are mature industries that are constantly changing. For the last three decades, refining schemes have indeed evolved considerably. They continue to change to adapt to numerous constraints which are not likely to decrease in the foreseeable future, and which are due to the need to limit consumption of petroleum products (in particular CO2-related issues), to have greater respect for the Environment and minimize refining costs. In this context, zeolites have an important role to play. The contribution of zeolitic catalysts to refining and petrochemicals is already substantial. We can hope for further achievements in the future through improvements to existing catalysts and the development of new catalysts, as the association of the properties of acidity and shape selectivity offered by zeolites is unique. These achievements could occur in a wide variety of domains, affecting not only the major processes of hydrorefining and conversion, but also smaller capacity, more specialized processes. But the development of any new process always comes up against the unavoidable need to be profitable and competitive, which is often a difficult obstacle to overcome in mature industries like refining and petrochemicals.
Acknowledgement I would like to extend my gratitude to a number of people at IFP for their help in providing technical and economical information: M. Baraqu6, O. Clause, L. Cuiec, G. Fournier, L. Kerdraon, J. Larue, A. Methivier,, X. Montagne, I. Prevost, and more particularly to J.B. Sigault. Additionnally, I would like to thank Mrs E. Ubrich for its precious assistance in library information searches.
References 1. D.W. Breck, W.G. Eversole, R.M. Milton, T.B. Reed, T.L. Thomas, J. Am. Chem. Soc., 78, 5963, 1956. 2. IFP source. 3. J. Laherr~re, P6trole et Techniques, 416, 61-79, Sept-Oct. 1998. 4. P6trole et Techniques, 421, 35-39, juil.-AoOt 1999. 5. N. Jestin-Fleury, P6trole et Techniques, 414, 37-41, Mai-juin 1998. 6. O. Godard, P6trole et Techniques, 421, 97-99, juil.-Aofit 1999. 7. J. Masseron, <>,Editions Technip, Paris, 1991. 8. S. Zehnder, P. Technon, P6trole et Techniques, 406, 50-54, 1997. 9. J. Cosyns, C. Cameron, Petr. & Techn., 411, 77-81, Nov.-D6c. 1997.
59 10. B. Firnhaber, G. Emmrich, F. Ennenbach, U. Ranke, Proceed. DGMK-Conf. (~The future Role of Aromatics in Refining and Petrochemistry )), Erlangen, Germany, 73-97, Oct. 13-15, 1999. 11. G. Fournier, P6trole et Techniques, 422, 62-64, Sept.-Oct. 1999. 12. Oil Gas J., Dec. 20 1999. 13. Oil Gas J., Dec. 25 1989. 14. Oil Gas J., March 26 1990. 15. Oil Gas J., Dec. 31 1979. 16. Oil Gas J., March 24 1980. 17. D. Benayoun, P6trole et Techniques, 406, 55-57, 1997. 18. P. Hodges, P6trole et Techniques, 423, 136-142, Nov.-D6c. 1999. 19. D. Seddon, Catal. Today, 15, 1-21, 1992. 20. R. Peer, D. Ackelson, O. Genis, S. Shorey, N. Orchard, P6trole et Techniques, 395, 58-74, Sept.-Oct. 1995. 21. J.C Guibet, E. Faure, ~ Carburants et moteurs, Technologies-Energie-Environnement ~, tomes 1 et 2, Editions Technip, 1997. 22. G.H. Unzelmann, 1992 NPRA Ann. Meet., New Orleans (Louisiana), paper AM-92-05, 35 p., March 22-24, 1992. 23. W.H. Keesom, O. Genis, C.P. Leubke, T.L. Marker, 1992 NPRA Ann. Meet., New Orleans (Louisiana), paper AM-92-26, 26 p., March 22-24, 1992. 24. P6trole et Techniques, 395, p. 28, mai-juin 1995. 25. G. Heinrich, S. Kasztelan, L. Kerdraon, in ~ Setting the Pace with IFP for the 21 st Century ~, IFP Publication, 143-168, june 1994. 26. K. van Leeuwen, Proceed. DGMK-Conf. ~ The Future Roles of Aromatics in Refining and Petrochemistry)), Erlangen, Germany, 7-20, Oct. 37-52, 1999. 27. E. Freund, P6trole et Techniques, 414, 44-51, Mai-juin 1998. 28. G. Heinrich, M. Valais, M. Passot, B. Chapotel, 13th World Petr. Congress, Buenos Aires, October 20-25, 1991. 29. G. Martino, P. Courty, C. Marcilly,, in (~Pespectives in Oil Refining ~), Handbook of Heterogeneous Catalysis, G Ertl, H. Knozinger, J. Weitkamp, Eds, Part B : Catalytic Processes, Vol. 4, 1801-1818, VCH a Wiley Company, 1997. 30. A. Douaud, C. Girard, P6tr. & Techn., 416, 7-14, Sept. Oct. 98. 31. C. Baudoin, P6trole et techniques, 422, 94-99, Sept. Oct. 99. 32. C. Dulout, P6trole et techniques, 422, 90-93, Sept. Oct. 99. 33. E.J. Swain, Sulphur, 22, 16-19, Sept.-Oct. 1992. 34. J. Vaquie, P6trole et techniques, 422, 100-102, Sept. Oct. 99. 35. M. Legrand, P6trole et techniques, 422, 103-105, Sept. Oct. 99. 36 M. Kitto, Sulphur, 258, 51-54, Sept-Oct. 1998. 37 ~ Facing the future ~, Sulphur, 258, pp 43, 45, 49, Sept-Oct. 1998. 38. Rapport n ~ 25 de l'Acad6mie des Sciences Fran~;aise, Oct. 1990. 39. From Web site of EPA (figures updated Aug. 2000). 40. O. Appert, P6trole et techniques, 421, p. 95-96, juil.-Aofit 1999. 41. P6trole et techniques, 421, p. 23-27, juil.-Aofit 1999. 42. M. Petit, P6trole et Techniques, 410, 67-68, Sept.-Oct. 1997. 43. A. Douaud, P6trole et Techniques, 426, 70-76, Mai-juin 2000. 44. H.P. Lenz, C. Cozzarini, (( Emissions and air quality >~,Warrendale (Pa.), Soc. Automot. Eng., 125p., 1999.
60 45. t~ Oil Information 2000 )),IEA Statistics, OECD/IEA, Paris, 2000. 46. J. Heinwood, A. Schafer, S6minaire Totalfina tt changements climatiques )), IPIECA, Paris,11-12 mai 1999, dans P & T, 421, p. 27, juil.-Aof~t 1999 47. M. Moret, P6trole et Techniques, 422, 68-73, Sept.-Oct. 1999. 48. J.B. Sigaud, P6trole et Techniques, 422, 89, Sept.-Oct. 1999. 49. J.B. Sigaud, Congr6s SIA 2000, Lyon (France), 14p., 10-11 Mai 2000. 50. J.P. Vettier, Conference at the ~ CEC-SAE Spring Fuels and Lubricants Meeting ~, Paris,19-22 june 2000. 51. C. Belorgeot, X. Boy de la Tour, A. Chauvel, S6minaire ~ Vers le 21 e si6cle avec les technologies de I'IFP ~), Paris, juin 1994. 52. G. Martino, C. Marcilly, Petrofina Chair, Leuven Summerschool on catalysis, Brugge, Belgium, Oct. 12-15, 1997. 53. C.A. Cabrera, CatCon 2000, Houston (TX), USA, June 12-13, 2000. 54. I.E. Maxwell, Cattech, 5-13, March 1997. 55. W. Weirauch, Hydroc. Process., 79 (2), 23, Feb. 2000. 56. Oil Gas J., p 53, Feb. 28, 2000. 57. Source CECA 58. A. Pfenninger, Proceed. Symp. on ~ Industrial Applications of Zeolites )), Oct. 22-25, 2000, Brugge, Belgium, Technol. Instituut vzw, 73-82, 2000. 59. C.G. Coe, Presentation at Symp. On ~ Industrial Applications of zeolites ~), Brugge, Belgium, Oct. 22-25, 2000. 60. M.T. Grandmougin, R. Le Bec, D. Plee, G. Dona, Proceed. Symp. on ~ Industrial Applications of Zeolites ~>,Oct. 22-25, 2000, Brugge, Belgium, Technol. Instituut vzw, 93104, 2000. 61. M.W Schoonover, M.J. Cohn, Topics in Catal., 13,367-372, 2000. 62. C.R. Marcilly, Topics in Catal., 13 (4), 357-366, 2000. 63. K. Tanabe, W.F. HOlderich, Appl. Catal. A : General, 181,399-434, 1999. 64. R.A. Sheldon, R.S. Downing, Appl. Catal. A : General, 189, 163-183, 1999. 65. M.G. Clerici, Topics in Catal., 13 (4), 373-386, 2000. 66. W. Htilderich, H. van Bekkum, in ~ Introduction to Zeolite Science and Practice )), H. van Bekkum, E.M. Flanigen, J.C. Jansen, Eds, Elsevier, Amsterdam, Stud. Surf. Sci. Catal.,, 58, 631, 1991. 67. P.B. Venuto, in ~ Progress in Zeolite and Microporous Materials, H. Chon, S.K. Ihm, Y.S. Uh, Eds, Elsevier, Amsterdam, 811-852, 1997. 68. M. Spagnol, L. Gilbert, R. Jacquot, H. Guillot, P.J. Tirel, A.M. le Govic, 4th Intern. Symp. Heterog. Catal. And Fine Chemicals, Basel, Switzerland, 1996. 69. S. Ratton, Chimica Oggi, 33-37, March-April 1998. 70. P.B. Venuto, Microp. Mater., 2, 297, 1994. 71. P.B. Venuto, P.S. Landis,, Adv. Catal., 18,259-371, 1968. 72. B. Coq, V. Gourves, F. Figueras, Appl. Catal A : General, 100, 69, 1993. 73. C. Moreau, F. Fajula, A. Finiels, S. Razigade, L. Gilbert, R. Jacquot, S. Spagnol, Catal. Org. React.,Dekker, p.51, 1998. 74. M. Noack, P. K61ch, R. Sch~ifer, P. Toussaint, J. Caro, I. Sieber, Proceed. Symp. on ~ Industrial Applications of Zeolites >~,Oct. 22-25, 2000, Brugge, Belgium, Technol. Instituut vzw, 25-34, 2000.
Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
61
Is Electron Microscope an Efficient Magnifying Glass for Micro- and Meso-porous Materials ? Osamu TERASAKI a'b'* and Tetsu OHSUNA ~ a: Deptartment of Physics and CIR, Tohoku University, Sendai 980-8578, Japan_ b: CREST, JST, Tohoku University, Sendai 980-8578, Japan c: Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan * Corresponding Author: [email protected]
Using electron microscopy(EM), we can solve three dimensional structures of microand meso-porous materials through newly developed methods based on electron crystallography. The underlying principle among diffraction, image and Fourier transformation for the methods, and a resolution of the method are discussed in terms of structure details we are interested in. An example of structure analysis for SBA-6 shows power of the methods, and future tasks will be discussed at the Conference.
1. INTRODUCTION
1-1. Microscope and Resolution The optical microscope is an instrument that uses lenses to produce enlarged images of small objects especially too small to be seen by the naked eye In an optical microscope, the spatial distribution of absorption or reflectance of light is enlarged. It is seldom, as far as we know, an optical microscope is used to obtain diffraction information except a conoscope. Big effort was paid to improve the resolution of optical microscope to observe smaller objects. However, the resolution of perfect lens(theoretical), Rth, is given from Rayleigh criteria as Rth =1.22 X/ct, (eq. 1) where ct and X are angular aperture size and wavelength. Necessary resolution comes from what kind of structural information we are interested in. The resolution of optical microscope is far below to resolve structure in atomic scale, as X is 3000-8000A for visible light and a is order of 1 (most of text books used semi-angle, or/2). Although the wavelengths of characteristic X-ray for ka radiation of 3d-transition metals are suitable range of 1.5-2.5 A for atomic resolution, we can not make a reasonable lens.
62 Electron has charge, and we can make an electromagnetic lens through the Lorentz force and hence an electron microscope(EM). Applying the de Broglie relation, the wavelength of electrons is determined by (A) = h/~/(2meV) -- ~/{150/V(volts)},
(eq. 2 )
where h, m, e and V are Planck's constant, electron mass, electron charge and accelerating voltage, respectively. ~, is 0.037 A at 100 kV and looks small enough to resolve structure in atomic scale if we can keep o~ to be order of 1. Is the resolution of electron microscope enough to resolve structures in atomic scale? In case of
electromagnetic lens, lens is not perfect with different kinds of aberrations. From geometrical optics, a point source will be imaged as not a point but a disk by a lens with spherical aberration. Disk diameter of confusion, R~ph,is given by Cs(ct/2) 3, where C, is a spherical aberration constant of the lens. Taking the effect of the aberration into account, the resolution R can be expressed as R = ~/{(Rth2+ R~ph2)}
(eq. 3)
as Rth and P~phare independent event each other. R~in = 0.9 (X3/4Cs1/4)
R takes minimum value
(eq. 4 )
at optimum angular aperture size t~opt - 1.54 (L/Cs)TM
(eq. 5 )
In other words, an effective value of t~ in eq. 1 for the electromagnetic lens is essentially given by a spherical aberration as 1.54(2qC~)TM, and is order of 10 -3.
The
attainable resolution is given by 0.9 (X3/4CsTM)and is 1.8 - 2.5 A range for most of 200 and 300 kV EMs. However, it is very hard to reach the resolution mentioned above for a case of zeolites(microporous materials), because they are so electron beam sensitive that we can not irradiate enough number of electrons onto them for taking HREM images. Therefore HREM is not enough to resolve atomic arrangement for zeolites[ 13]. Diffraction study is another and principal approach for structural study. It is well known that X-ray diffraction(XRD) can give average structural information with very high resolution and XRD has been used to solve structure of zeolites in atomic scale and also to show long range order in mesoporous materials. Using EM, however, we are able to observe both electron diffraction(ED) patterns and images. ED is free from the aberration effect and provides like XRD structural information with much higher spatial resolution than HREM images, and we can obtain ED data with much smaller
63 number of electrons. Electrons are scattered through the interaction with the electrostatic potential formed by the electrons and nucleus of the constituent atoms. The scattering power of atoms for electrons is called as the atomic scattering factor and is approximately 104 times as large as that for X-rays. This suggests that compared to X-ray scattering, smaller scatterers can provide sufficient structural information and thus much smaller objects(ca. 10-8 times) can be studied with electrons. It is to be noted here that we could choose a proper small crystalline area in image mode and obtain single crystal diffraction information only from the same area, and that EM is very powerful for micro- and meso-porous materials as they are mostly synthesized as panicles of c a . 1 lam in size. In this paper, we will give general background of electron crystallography to solve micro- and mesoporous structures and show EM is unique and powerful technique by a few examples. At the Conference, other relateds will be also discussed. 1-2. Diffraction, Image and Fourier Transform
Figure 1 shows a schematic drawing, which gives length scale of our interests. Crystal is a three-dimensional (3-d) periodic array of unit cells, each of which contains a same arrangement of atoms. Therefore to solve atomic arrangement, that is, to determine distribution of scattering density, V(r), in a unit cell is a central problem for Resolution of Electron Mkroseopy I
I'
I
Wave length
Wave length of X-ray
Wave length of light
of eleclron
V lOOA t
2 A,
I
+
0.1.~
lit
I
I
v
Structures of Mesoporous Diameters of Pore & Cage are 20-500 A
Framework Strueture of Zeolites Bond di st~ces, T-O = 1.6 A T- (O) -T= 3 A
Fig. 1
Atomic Coordinates Atomic coordinates are obtained by statistical treatment from many rdlecti ons up to large scattering vectors.
Schematic Length Scale
d (X)
64 structure analysis. V(r) can be obtained from analysis of crystal structure factor(CSF), F(h), for h (h,k,1) reflection, which are Fourier coefficient of V(r) as F(h) =
~ V(r) exp 2hi h r d r = [ F(h) [ exp{ i 0(h)},
(eq. 6)
where 0(h) is phase of CSF. CSF is complex in general. A position r in the unit cell can be given by fractional coordinates with lattice vectors a, b, c, as r = xa+yb+zc.
(eq. 7)
Reciprocal vector h is given by a set of (h,k,l) and reciprocal lattice vectors, a*, b*, c*, h=ha*+kb*+lc*
.
(eq. 8)
Once, 3-d data set ofF(h) is obtained then structure V(r) can be determined by an inverse Fourier transform straightforwardly as V(r) = ~ F(h) exp(- 2rcir h) dh
(eq. 9)
.
Diffraction intensity I(h) for h reflection is given by I(h) = F(h)* F(h) = [I F(h) I ]2
(eq. 10)
and looses phase information. Therefore we can obtain only absolute value, moduli, I F(h) I from diffraction intensity. For a centrosymmetric crystal, we can make F(h) real, that is phases of F(h) are either 0(+) or ~(-)by taking an origin at inversion centre for eq. 7.
Hereafter, we will treat only centrosymmetric crystals for simplicity. In
order to show an importance of the phases of CSFs for obtaining correct
ceelxl
~.
,
"~_~.f
f
structure V(r), one dimensional model system is shown schematicaly in Fig. 2. Two structures among a
i[
0=0
]
"?
-t
number of possible ones, (a) and (b), cod3xl
give exactly the same diffraction intensities, only difference between
$=0
/-\ f \ ,/~x / v \./ \ ~=g
the two is phases 0(h) in F(h), that is, phases of g, 2g, 3g reflections are +,
(a) cos[x] + cos[2x], cos[3x]
(b) cos[x]- cos[2x]- cos[3x]
4
+, + for case of (a) and + , - , - for case of (b). After determining space group,
,
2
_(a) 9
(b
r O -I
two major approaches to solve the
-Z
Fig. 2 Importance of phases in CSFs is shown schematically for one dimensional case.
65
Fig. 3 Flow chart of Structure Solution structure by tackling phase problem are schematically shown in Fig. 3. (1) Through ED patterns: Attempts to find phases have been based on a trial-and-error process. CSFs were calculated for a trial structure and compared with intensity I(h) under the measure of agreement, so called reliability index Reac-Patterson function method or heavy-atom method helped greatly to reduce number of trial structures by giving information of interatomic vectors of main scatterers or of heavy-atom positions. Direct method opened new fields for the process in estimate of the phases ab initio from
66 the magnitudes of the structure factors. In order to apply this method, intensities for many independent reflections must be measured. (2) Through HREM images: HREM images carry phase information, and in this case we can determine phases uniquely without pre-assumed structure models. Now, let us think by Figs..2 and 3 a relation between diffraction and image, and information limit for phases by EM image. Electrons are incident to a crystal as a plane wave. We will take the direction of incident electrons to be z-axis. The role of the objective lens is to transfer Fourier transform of wave field at the exit of the sample for a set o f g reflections with CSFs of F(g) as shown in Fig. 2, i.e., Franhoufer diffraction, to the back focal plane of the lens. The lens further (inverse) Fourier transforms the diffraction to image at the image plane. ED patterns and EM images are observed as an intensity distribution in reciprocal space and real space, respectively. From this procedure, it is obvious EM images carry phase information of CSFs, but the information of CSFs within a range given by Ctopt (eq. 5) is transferred (see Fig. 3).
2. Mesoporous materials: The local structure variations in mesoporous materials are common and produce a small number of reflections and large peak widths in powder XRD patterns, even though the materials show nice crystal morphology. This situation can be shown by an example for MCM-48 in Figure 4. Two structural characteristics of the meoporous materials are clearly observed in the powder XRD pattern(Fig. 4a), where (i) disorder on the atomic scale (short-range) can be seen as diffuse intensity at medium range of scattering angles and (ii) distinct order on the mesoscopic scale (long-range) can be seen
Fig. 4 Powder XRD pattern and SEM imageof MCM-48.
67 as a few sharp diffraction peaks at small scattering angles. SEM image of MCM-48(Fig. 4b) clearly shows nice crystal morphology which is commensurate with point symmetry ofm-3m. By noticing 3-d mesoporous material as crystalline, we have developed a new method for solving the structures with meso-scale ordering without assuming any structural models based on section 1-2. The resolution for the structure is primarily limited by the quality of the HREM images, which depends on the long-range meso-scale ordering and the treatment of the EM image processing.
Further progress may give better
Fig. 5 HREM images of SBA-6 and corresponding Fourier diffractograms
68 resolution, but no change in conclusions will be necessary about structure because the validity of a solution does not depend on the resolution[4,5]. Figure 5 shows a set of HREM images of SBA-6 together with Fourier diffractograms. From image we can choose thin areas
which
dynamical
are
scattering
free and
from the
Fourier diffractograms from thin regions are also shown in Fig. 5. From observations in extinction conditions from the diffractograms and in point group symmetry from SEM image, the space group of SBA-6 was uniquely determined to be Pm-3n. Basic structure of SBA-6 can be obtained only from two HREM images of [100] and [110] incidences. The images of [ 111 ]
and
[210]
incidences
improved fine details of structures
Fig. 6
Structure solution of SBA-6. Pm-3n.
of cages and tunnels between them[5]. The cages are arranged in A3B type, where the A-cage is the larger with a diameter of 85 ,/~ at (1/2,0,1/4), (1/2,0,3/4), (0,1/4,1/2), (0,3/4,1/2), (1/4,1/2,0) and (3/4,1/2,0), and the B-cage is the smaller with a diameter of 73 fit at (0,0,0) and (1/2,1/2,1/2). A B-cage is surrounded by 12 A-cages that are connected through openings of 20/k, while the openings between A-cages are about 33 x 41 A. The materials synthesized in the spaces of mesoporous throw us new challenging problems to solve their structures by EM, and it will be discussed at the conference.
3. Zeolites:
Now we can measure ED intensities easily by using CCD camera or imaging plate as they have larger dynamic range and better linearity of output to input electrons than photographic film. Applying "Direct method" to collected ED intensities of 326 independent reflections from 11 zone axes, we could solve unknown structure of
69 zeolite SFE(SSZ-48) from very small crystal[6]. As zeolites have low density, kinematical treatment in diffraction is a good approximation for analysis of ED intensity distribution, if specimens are thinner than a few hundreds A. This is not so difficult conditions for zeolites if we can obtain as a single(pure) phase, Therefore this method is very powerful.
Fig. 7 HREM images of ETS- 10
70 Once a high quality HREM image is obtained, we can build important structural units and geometrical relations between them by making plastic bond-models. A clear example is shown here for ETS-10, which contains many different types of defects. It was confirmed from ED patterns and HREM images that ETS-10 has 4-fold symmetry in projection along z-axis and that the projected structures along x- and y-axes are identical. An HREM image(Fig.7a) gives important pore arrangement and the framework connectivity, and hints to build a primary structure unit(Fig.8 a). Fig. 7b shows surface structure suggesting that a rod is a secondary building and is growth unit in ETS-10(Fig. 8b). An ideal structure was determined from the observations as shown in Fig.8c[7,8,9]. This analysis requires deep knowledge of both structure and EM.
Fig. 8 Schematic drawings of framework structure of ETS-10
Recently we have developed a new powerful method for obtaining structure solutions of zeolites by combining HREM images and ED intensity data[ 10]. This will open up new field for the structure analysis of zeolites, however, we should continue to develop the method of solving structures further in order to make E M better magnifier towards atomic resolution.
4. Acknowledgments The authors greatfully acknowledge CREST, JST for financial support. We thank P. Wagner, A. Carlsson, Y. Sakamoto, M. Kaneda, Z. Liu, K. Hiraga and T. Tsubakiyama for their contributions.
71 References and Notes
[1] O. Terasaki. Molecular Sieves, Science and Technology. Vol. 2, pp71-112., Eds by H.G. Karge & J. Weitkamp, Springer-Verlag, Berlin, 1999. [2] O. Terasaki & T. Ohsuna. Catlysis Today 23(1995), 201-218. [3] O.Terasaki, T.Ohsuna, N.Ohnishi & K.Hiraga. Current Opinion in Solid State & Materials Science 2(1997), 94-100. [4] A.Carlsson, M. Kaneda, Y. Sakamoto, O. Terasaki, R. Ryoo & H. Joo J. Electron Microscopy. 48 (1999), 795-798. [5] Y. Sakamoto, M. Kaneda, O. Terasaki, D.Y. Zhao, J.M. Kim, G. Stucky, H.J. Shin & R. Ryoo. Nature 408 (2000), 449-453. [6] P. Wagner, O. Terasaki, S. Ritsch, S.I. Zones, M.E. Davis and K. Hiraga. J. Phys. Chem. B103 (1999), 8245-8250. [7] M.W. Anderson, O. Terasaki, T. Ohsuna, P. Phillppou, SP MacKay. A. Ferrelra, J. Rocha & S. Lidin: Nature 367(1994), 347-351. [8] T. Ohsuna, O. Terasaki, D. Watanabe, M.W. Anderson & S. Lidin: Studies in Surface Science and Catalysis, Vol 84, 1994, 413-420. [9] M.W. Anderson, O. Terasaki, T. Ohsuna, P.J.O Malley, P. Phillppou, SP. MacKay. A. Ferrelra, J. Rocha & S. Lidin: Phil. Mag 71(1995), 813-841. [ 10] T. Ohsuna et al., in preparation
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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
73
Delaminated zeolites as active catalysts for processing large molecules A. Corma* and V. Forn6s Instituto de Tecnologfa Qufmica, UPV-CSIC, Universidad Polit6cnica de Valencia, Avda. de los Naranjos s/n. 46022 Valencia, Spain Zeolite nanolayers have been obtained by delaminating the lamellar precursors of four zeolites. These materials present very high well structured extemal surface areas larger than 600 mZ.gl. Catalytic active sites can be introduced during the synthesis or by post-synthesis treatments, yielding active and selective catalysts for processing large size molecules of interest in oil refining and for the production of fine chemicals. 1. INTRODUCTION Zeolites have shown great utility as catalysts in the field of oil refining, petrochemistry and in the synthesis of chemicals and fine chemicals (1-3). In some cases shape selectivity effects are highly desired when using zeolites, while in others the main objective is to replace liquid acids using instead the environmentally more friendly solid acids. In this second case, there is a continuous interest to find molecular sieves with large and ultra-large pores that can convert bulky reactant molecules. If this could be achieved, the impact of zeolites would be even more important in processes such as fluid catalytic cracking (FCC), hydrocracking, hydrotreating, and in the production of chemicals and fine chemicals. Up to now, zeolites with 14 member ring (MR) pores are the ones with the largest pore synthesised (4,5). However, in these structures the pores are unidirectional and offer little advantage with respect to the tridirectional 12 MR Y and Beta zeolite for processing large molecules (6). Recently, mesoporous molecular sieves with different topologies have been synthesised (7-9). They show no short range order and the catalytic behaviour is closer to that of an amorphous silicaalumina with a narrow pore size distribution, than to a zeolite. There is then incentive to develop zeolitic materials that while keeping the short range crystallinity of zeolites, can have the accessibility of silica-alumina towards very large reactant molecules. One possibility along this direction is to synthesise small zeolite crystals (nanocrystalline zeolites) (10) that show a high ratio of external to internal surface, with enhanced possibilities to adsorb large reactant molecules on the external surface of the crystallites. While we have seen that this, can be an interesting approach in some cases (11), we have recently explored another direction (12,13) which involves the preparation of lamellar zeolites whose structure is subsequently delaminated, making accessible through the external surface all the potential active sites. The main difference between these type of materials and the mesoporous molecular sieves of the
74 MCM-41 type is that in the nanocrystalline and delaminated zeolites there is short-range order and consequently the active sites are of zeolitic nature. 2. DELAMINATED Z E O L I T E STRUCTURES Up to now, we have delaminated four different lamellar zeolitic precursors which have generated the materials named as ITQ-2, ITQ-6, ITQ-18 and ITQ-20 (12,13). The first one, ITQ-2, was obtained by delaminating a MWW zeolite precursor (14) while ITQ-6 and ITQ-20 were prepared by delaminating laminar precursor of ferrierite (15) and MCM-4"7 (16,17), respectively, while the structure of ITQ-18 is still unknown to us. The artist view of the structure of the two first material is presented in Figure 1.
Fig. 1. Artistic view of the structure oflTQ-2 and ITQ-6 delaminated zeolites. As a general procedure, the lamellar precursors of zeolites are swelled, at the adequate pH, using an alkyl ammonium bromide, or even an amine or an alcohol can also be used, to separate the layers. After this the swelled material can be delaminated by means of ultrasound, freezdrying, or by vigorous stirring. The "in situ" delaminated material can form an slurry or a paste with a matrix component and a binder, and the final product can be spry dried or extruded, respectively. If desired, the pure delaminated materials can be recovered by centrifugation. Activation is carried out by extracting the organics in liquid phase, or by decomposing them by calcination in air at 500~ It has to be noticed that these materials are stable upon calcinations at 700~ As one can expect, the X-Ray diffractogram of delaminated zeolites, show a small number of peaks, which are due to the reflections along the two main dimensions of the layers, while those due to the regular ordering of layers one above the other have disappeared owing to the delamination. More specifically (Fig. 2), in the case of ITQ-2 the XRD does not show the 001 and 002 peaks at 20=3-7 ~ while in the case of ITQ-6 the hOe reflections have practically disappeared.
75
,
,
,
,
,
10
0
20 20
,
,
30
,
,
.
40
0
.
.
.
.
.
10
.
.
20 20
.
30
40
Fig. 2. XR diffractograms of MWW and ferrierite (a,a'), their precursors (b,b'), and the delaminated ITQ-2 and ITQ-6 (c,c').
140 '
9
]-]
120 9
g
[ D
~
12MR
cavities
140
!/
120
[ 60.
10MR pores
k k ==
9
," ." ==
9ITQ6 9FER
100 -
80'
I
100'
10MR pores
&&
i
9
< 40-
40'
;.-'.." 0
1E-06 0.00001 0.0001 0.001 0.01
0.1
P/Po (logarithmic scale)
0 0.000001 0.00001 0.0001
0.001
0.01
0.1
PIPo (logarithmic scale)
Fig. 3. Argon isotherms of MWW and ferrierite (a,a'), their precursors (b,b'), and the delaminated ITQ-2 and ITQ-6 (c,c').
76 While the IR and 29SiMAS NMR spectra are consistent with the delaminated structure of ITQ-2 and ITQ-6, the Argon isotherms represented as a function of log P/P are highly informative on the changes in topologies experienced during delamination (Fig. 3). It can be seen there that ITQ-2 does not show the adsorption corresponding the large 12 MR cavities characteristics of the MWW structure, while preserves that of the intralayer 10 MR circular channels. Meanwhile, in the case of ITQ-6, the adsorption at the 10 MR pores of ferrierite has practically disappeared. It appears then that during the delamination of lamellar zeolitic precursors we have produced disordered individual sheets of crystalline zeolitic material that may be forming a "house of cards" type of structure, leaving mesopores in between them and allowing accessibility of reactants to the external active sites. This gives to delaminated zeolites extremely large external surface areas (Table 1) that are highly desirable for many catalytic processes. Notice that the area remains stable at high calcinations temperatures and even after steaming at 650~ Table 1 Surface area determined by N2 adsorption after calcination at 550~ for 3 hours. Material SBET(m2g"l) SEXT(m2g"1) MWW 452 97 ITQ-2 841 776 Ferrierite 278 53 ITQ-6 620 575 The resultant delaminated materials, when are prepared in a silica-alumina form, show strong Brtinsted acidity of the zeolitic type, which are much stronger than those of MCM-41 and accessible to large molecules, as indicated by the adsorption of 2,6-di-tert-butylpyridine. 3. CATALYTIC P R O P E R T I E S
3.1. Oil refining and petrochemistry The accessibility to acid sites of large oil molecules is shown by comparing the relative rates of MWW and ferrierite with respect to the corresponding ITQ-2 and ITQ-6 for cracking diisopropyl- and triisopropyl-benzene, and vacuum gasoil (Table 2). The results clearly show, that despite the fact that the delaminated zeolites have a lower number of total acid sites, as measured by pyridine adsorption, due to some dealumination occurring during the preparation, their activity is much higher, owing to a better accessibility of the reactants to the acid sites.
77 Table 2 Cracking activity of non delaminated and delaminated zeolitic materials Kinetic rate constants (s "l) Material DiisopropylTriisopropylVacuum Benzene Benzene Gasoil MWW 0.10 -0.025 ITQ-2 0.18 -0.050 Ferrierite -0.03 -ITQ-6 -0.14 -a Brrnsted acidity measured by pyridine, after desorbing at 523 K and 10 -2 Tor.
Acidity a 24 15 19 9
One may reasonably think that these materials are probably too costly and probably not enough stable to be commercially used in FCC units, but they may have a possibility as a component of hydrocracking catalysts. In this case, it would be highly desirable to have a material which could combine the good selectivity for diesel of amorphous silica-alumina, with the high activity of zeolites. It appears then, that delaminated zeolites could accomplishes these two objectives. Thus, we present here (Fig. 4) the results obtained during mild hydrocracking of vacuum gasoil on NiMo/ITQ-2, NiMo/USY, NiMo/ASA, NiMo/7-A1203, all catalysts containing 12 wt% MoO3 and 3 wt% NiO.
Fig. 4. Hydrocracking (HC) conversions obtained for the different catalysts as a function of the reaction temperature. Reaction conditions: 3.0 MPa. 2 h l WHSV and 1000 H2 (stp)/feed ratio: ( 9 ) NiMo/ITQ-2. (m) NiMo/USY. (A) NiMo/ASA. ( v ) NiMo/),-A1203. Figure 4 presents hydrocracking conversion at 3.0 MPa, 2 h -1 ~rHSV, 1000 H2 (stp) feed ratio, and different reaction temperatures. It can be seen there that NiMo/ITQ-2 shows the highest activity, closely followed by NiMo/USY, and in any case the activity of the former is much higher than that of NiMo/SiO2-A1203. The product selectivity at 50-55% of HC conversion is compared in Figure 5. As expected, NiMo/ITQ-2 presents a selectivity
78 behaviour which is intermediate between NiMo/SiO2-A1203 and NiMo/USY. In this way, NiMo/ITQ-2 it produces more diesel and less gases than NiMo/USY, showing promise as a hydrocracking catalyst, since it combines the high activity typical of zeolite-based catalysts with the good selectivity of amorphous catalysts.
Fig. 5. Selectivity to the different hydrocracked fractions obtained at ca. 55% hydrocracking conversion over NiMo-containing catalysts: (m) NiMo/ASA. ~ )NiMo/USY. (Fq)NiMo/ ITQ-2. Gases: C~-C4. Naphtha: C5-195~ Middle distillates: 195-360~ 3.2. Delaminated zeolites for fine chemicals
There are cases in where the production of fine chemicals involves the use of large reactant molecules or the formation of bulky products. In both cases, zeolites show limitations either for the reactants to penetrate into the pores, or for products to diffuse outside of the pores. In this case one can certainly decrease the crystallite size of the zeolite or even to use mesoporous materials to favour diffusivity. However, will show some cases in where there is a clear benefit of using delaminated zeolites over the other two types of materials. There is an important number of acetals that are used as fragrances. The synthesis of acetals is generally carried out by reacting aldehydes with alcohols. These are reactions which involve mild acid sites as catalysts. Here, we present firstly the synthesis of acetals from aldehydes of different molecular sizes on three catalysts, i.e. Beta zeolites with different crystallite sizes, mesoporous MCM-41, and the delaminated ITQ-2 material. The results presented in Table 3 clearly show that for small size acetals that can penetrate inside the micropores of Beta, this is the most active catalyst owing to its larger amount of acid sites, and also to concentration effects within the micropores that can favour bimolecular reactions. However, when the size of the aldehyde increases, the activity of Beta zeolite, even within crystallite sizes as small as 60 nm, is strongly diminished and is lower than that of MCM-41 and ITQ-2. In this case, the activity of the delaminated zeolite is clearly superior to either Beta of MCM-41 as a result of combining high accessibility to reactants with acid sites of zeolitic nature. More specifically, the synthesis of 2-methyl-2-naphthyl-4-methyl-l,3-dioxolane which has an orange blossom fragrance, was obtained by reacting 2-acetonaphthanone with 1,2propanediol at 419K in a batch reactor.
79 Table 3 Synthesis of acetals on different zeolitic materials
' II Rl u CH-C,,
H
R1
R20CH 3 Rn---- H - , I O C H 3 Solid Catalysts H
1-3
R2
1 CH3(CH2)4 H 2 Ph CH 3 Ph 3 Ph
(Eq. 1)
la-3a
Initial rates and conversion for the acetalization of aldehydes 1, 2 and 3 with trimethyl orthoformate ~TMOF) over different acid catal~,sts b. Catalysts
1
2
ro(h'l) Conversion a ro(h-1) Conversion a
3 ro(h-1)
Beta (~0.06) 200 78 120 65 (Si/Al=l 8) Beta(~0.86) 177 75 67 43 (Si/Al=18) Beta (t~ 0.1 ) 450 90 108 40 (Si/A1-50) MCM-22 (Si/A1= 50) 150 40 55 23 ITQ-2 (Si/AI= 50) 420 95 330 85 MCM-41 ~Si/A1 =40) 210 80 180 70 a)lh reaction time. b) Reaction conditions: aldehyde (2.5 mmol), TMOF (30 mg) in 25 ml CC14 at 78~
Conversion a
48
15
10
6
48
27
50 210 180 (12.7 mmol),
25 75 71 catalyst
Table 4 Synthesis of Blossom oranged. Reaction conditions: 7.4% wt/wt of catalyst respect to 2acetonaphthanone, 419 K, volume ratio: toluene/2-acetonaphthanone = 26.6.
Catalyst ITQ-2 MCM-22 HI32a H~3 b MCM-41
Si/A1 50 50 15 15 15
a Commercial sample, b Nanocrystalline zeolite
Yield of Blossom oranged Reaction Time lh 3h 32 80 5 12 4 5 24 45 9 24
80 The reaction was carried out using Beta, Beta nanocrystalline, MCM-41, and ITQ-2 as catalysts. The results presented in Table 4 show that ITQ-2 is more active than the nanocrystalline Beta, despite the fact that the number of acid sites is much smaller in the former, and much more active than MCM-41. The selectivity to the desired product on ITQ-2 is practically 100%. The synthesis of lactames has interest for the production of chemicals and fine chemicals. In the case of more bulky lactames derived from cyclodedecanone-oxime and cyclooctanone-oxime, they are used for producing nylon-12 and for the preparation of the precursor of azacycloalkanediphosphonic derivates which have pharmaceutical interest for the treatment of Ca 2+ metabolism disorders, respectively. In this case, the conversion of cyclododecanone and cyclooctanone oxime were done by the Beckman rearrangement in liquid phase, in a batch reactor at 403 and 433 K, respectively, with a catalyst to oxime ratio of 1:2 wt.wt ~, and chlorobenzene and sulfolane as solvent, respectively. The results reported in Table 5 show a higher activity for the delaminated ITQ-2 sample. Moreover, adsorbed products are easier to be removed from the surface of the delaminated material, as indicated by the smaller amount of organic left on the solid after reaction which was in the case of cyclododecanone-oxime, 2, 3 and 5 wt% for ITQ-2, MCM-41 and Beta, respectively. By optimising temperature and solvent, conversions higher than 95% with selectivities to the lactames > 98% can be obtained with ITQ-2. Table 5 Synthesis of the lactames of cyclooctanone and cyclododecanone oxime at 430~ minutes reaction time on various catalyst with a Si/AI ratio of 50.
Catalyst ITQ-2 MCM-41 Beta (0.1 lam)
and 90
Conversion (%) Cyclododecanone oxime Cyclooctanone oxime 98 82 67 60 32 26
3.3. Delaminated zeolites as catalysts supports Improving the quality of the Light Cycle Oil (LCO) produced in the FCC unit can be a necessary task to meet future diesel specifications. In order to improve the quality of LCO, polyaromatics should be hydrogenated and sulfur reduced. Owing to its high sulfur content, a dual-stage hydrogenation process has to be used where the feed is first hydrotreated to reduce the sulfur content, and then hydrogenated using a noble metal catalyst in the second reactor. A hydrotreated LCO which contained 400 ppm sulfur, and 68% aromatics with the distribution between mono, di and tri + aromatics given in Figure 6, was hydrogenated using Pt on different supports, i.e. amorphous silica-alumina, USY zeolite and ITQ-2. Acid supports were used here to increase the thioresistance of the catalysts. The results (Fig. 6) show that Pt/ITQ-2 gives the highest aromatics reduction, being mainly the tri +- and di-aromatics the ones reduced.
81
Fig. 6. Total aromatics content and aromatics distribution obtained in the hydrogenation of a hydrated LCO (HT-LCO) over the different Pt supported catalysts. Reaction temperature: 300~ The values corresponding to the HT-LCO feed are also included for comparison. ( D ) Mono-aromatics. (El) Di-aromatics. ( I ) Tri § The ferrierite delaminated ITQ-6 material has been successfully used as a support for enzymes (18). More specifically, ~-galactosidase from Aspergillus Oryzae, and penicillin Gacylase have been electrostatically and covalently immobilised on ITQ-6, resulting with enzyme catalysts highly active and stable. The advantage of delaminated zeolites as enzyme support is derived from the well structured external surface in where the silanol groups are regularly distributed. This allows a multipoint attachment between the enzyme and the supports, perhaps involving the most reactive groups of the protein surface. 4. CONCLUSION A new type of materials has been developed by delaminating the lamellar precursors of some zeolites. These materials show external surface areas > 600 m2.g"1 from where active sites can be accessible to very large molecules. If on one hand delamination eliminates geometrical shape selective properties of zeolites, it allows on the other hand to dispose of catalysts with the good reactant accessibility of mesoporous materials, but with the stability and active sites characteristics of zeolites. The very large and well structured external surface area can be specially suited for supporting different catalytic functions, which include, among others, metals, transition metal complexes and enzymes. 5. R E F E R E N C E S
1. A. Corma, Chem. Rev., 95 (1995) 559. 2. I.E. Maxwell and W.H.J. Stork, Stud. Surf. Sci. Catal., 58 (1991) 571. 3. R.A. Sheldon and H. van Bekkum (eds.), Fine Chemicals Through Heterogeneous Catalysis., Wiley-VCH, Weinheim (2001). 4. K.J. Balkus, Jr., A.G. Gabrielov and N. Saudler, Mater. Res. Soc. Symp. Proc., 368 (1995) 359. 5. P. Wagner, M. Yoshikawa, M. Lovallo, K. Tsuji, M. Taptsis and M.E. Davis, Chem. Commun. (1997) 2179.
82 J. Martinez-Triguero, M.J. Diaz-Cabafias, M.A. Camblor, V. Fom6s, Th.L.M. Maesen and A. Corma, J. Catal., 182 (1999) 463. J.S. Beck, J.C. Vartulli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgings and J.L. Schlenker, J. Am. Chem. Soc., 114 (1992) 10834. A. Monnier, F. Schilth, Q. Huo, D. Kumar, D. Margolese, R. S. Maxwell, G. D. Stucky, M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke and B. F. Chmelka, Science, 261 (1993) 1299. A. Corma, Chem. Rev., 97 (1997) 2373. 10. B.J. Schoeman, J. Sterte and J.E. Otterstedt, Zeolites, 14 (1994) 110. 11. M.A. Camblor, A. Corma, A. Martinez, V. Martinez-Soria and S. Valencia, J. Catal., 179 (1998) 537. 12. A. Corma, V. Fom6s, S.B. Pergher, Th.L.M. Maesen and J.G. Buglass, Nature, 396 (1998) 353. 13. A. Corma, U. Diaz, M. Domine and V. Fom6s, Angew. Chem. Int. Ed., 39 (2000) 1499; and J. Am. Chem. Soc., 122 (2000) 2804. 14. S.L. Lawton, A.S. Fung, G.J. Kennedy, L.B. Alemany, C.D. Chang, G.H. Hatzikos, D.N. Lissy, M.K. Rubin, H.J.C. Timken, S. Stenemagel and D.E. Woessner, J. Phys. Chem., 100 (1996) 3788. 15. L. Schreyeck, P.H. Caullet, J.C. Mougenel, J.L. Guth and B. Marler, Chem. Commun. (1995)2187. 16. E.W. Valyocsik, US Patent N ~ 5 068 096 (1991). 17. A. Burton, R.J. Accardi, R.F. Lobo, M. Falcioni and M.W. Deem, Chem. Mater., 12 (2000) 2936. 18. A. Corma, V. Fom6s, J.L. Jordh, F. Rey, R. Fem6.ndez-Lafuente, J.M. Guis6.n and C. Mateo, Chem. Commun. (2001) in press. .
Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
83
Pentasil zeolites from Antarctica" from mineralogy to zeolite science and technology A. Alberti a, G. Cruciani a, E.Galli b, S. Merlino c, R. Millini d, S. Quartieri e, G.Vezzalini b, S. Zanardi a aDipartimento di Scienze della Terra, Universith di Ferrara, Italy. bDipartimento di Scienze della Terra. Universith di Modena e Reggio Emilia, Italy. CDipartimento di Scienze della Terra, Universit/l di Pisa, Italy. dEniTecnologie S.p.A., S. Donato Milanese, Italy. eDipartimento di Scienze della Terra, Universit/l di Messina, Italy.
SUMMARY In the course of a systematic investigation of zeolites from Northern Victoria Land, Antarctica, a large number of zeolitic species was identified in the Jurassic Ferrar Dolerites of Mt. Adamson. Noteworthy was the presence of three new zeolites: gottardiite, the natural counterpart of the synthetic NU-87, terranovaite, and mutinaite, the analogue of ZSM-5, as well as the two very rare zeolites tschernichite, the counterpart of zeolite beta, and boggsite. The chemical and crystallographic properties of these natural materials were compared with those of their synthetic analogues. The tetragonal and monoclinic polymorphic phases, intergrown in the beta zeolite, were isolated and structurally refined in tschernichite crystals, which differ by crystal size, morphology and chemistry. The occurrence of these natural zeolites demonstrates that the chemical existence field of their synthetic counterparts is larger than that argued up to now, and that their synthesis can be obtained in the absence of an organic template.
1. INTRODUCTION It is well known that zeolites containing a high proportion of five-membered rings of tetrahedra in their framework are widely used in heterogeneous catalysis; these include synthetic ZSM-5, ZSM-11, beta, theta-1, NU-87, the synthetic analogues of natural mordenite and ferrierite and the natural zeolite heulandite. During an investigation of zeolites from Northern Victoria Land, Antarctica, numerous zeolitic species, among which the pentasils are predominant, were found in the Jurassic Ferrar Dolerites of Mt. Adamson: heulandite, stellerite, stilbite, mordenite, erionite, levyne,
84 cowlesite, phillipsite, chabazite, epistilbite, ferrierite, analcime and, particularly interesting, the rare zeolites boggsite and tschernichite, the natural counterpart of zeolite beta [1]. Noteworthy is the presence of three new pentasil zeolites: gottardiite [2], the natural counterpart of NU-87, terranovaite [3] and mutinaite [4], the natural counterpart of ZSM-5. Very striking is the occurrence at Mt. Adamson of so many natural analogues of important synthetic zeolites and of two minerals (boggsite and terranovaite) still lacking their synthetic counterpart. The aim of this contribution is to highlight the impact that the study of mineral zeolites can have on zeolite knowledge. In particular: a) natural zeolites usually occur in crystals which are large enough for single-crystal X-ray diffraction studies; these investigations allow structural information to be obtained which is far more detailed and accurate than that gathered by powder diffraction data or other experimental techniques; b) the counterparts of synthetic zeolites found up to now in nature usually have significantly different Si/A1 ratios and extraframework contents. This shows that the chemical existence field of these topologies is wider than that up to now deduced from the compositions of the synthesised phases; it should also be borne in mind the extent to which chemical characteristics can influence the technological properties of the materials, and how much detailed structural information is essential for their comprehension. Below we describe the crystal-chemistry of the new and rarest zeolites from Mt. Adamson, with a particular emphasis on the most recent results conceming the structural features of the tschernichite-type mineral and a comparison with its synthetic analogue beta.
2. GOTTARDIITE The first of the new natural zeolites found at Mt. Adamson was gottardiite [2]. The crystals occur as thin lamellae, pseudo-hexagonal in shape or elongated along the a axis. The crystals, transparent and colorless, rarely occur in isolation; more frequently they form aggregates of a few individual crystals. The chemistry of gottardiite (unit cell content: Na2.sK0.zMg3.1Ca4.9Al18.8Sil17.zOzvz'93H20) is characterized by a high magnesium content and a very high Si/A1 ratio (6.2) compared with other natural zeolites. Gottardiite shows a high thermal stability and very high re-hydration capacity; the mineral quickly and completely regains its weight loss at temperatures of up to 800~ whereas at 1100~ its rehydration capacity becomes zero, probably due to the framework destruction occurring in this temperature range [2]. Its fast and complete rehydration suggests that no T-O-T bridge breaking occurs during dehydration [5]. The mineral is orthorhombic (a=13.698(2), b=25.213(3), c-22.660(2) A), with topological symmetry Fmmm and real symmetry Cmca [6]. In the Fmmm symmetry there are five non-symmetry-related sites on inversion centers. In this topological symmetry two oxygen atoms lie on two of these 1, causing energetically unfavourable T-O-T angles of 180 ~ In the Cmca sp.gr, these two inversion centers disappear, while the other three remain. This situation is common to all zeolites where, in the topological symmetry, framework oxygens lie on centers of symmetry [7].
85 The topology of gottardiite, which has not been found in other natural zeolites, is the same as that of synthetic zeolite NU-87 [8]. This is more evident if we describe the NU-87 unit cell not on the basis of the conventional monoclinic unit cell P21/c (a = 14.324 A, b = 22.376 A, c= 25.092 A, 13=151.52~ ), but in the pseudo-orthorhombic unit cell C l l 2 / / b (a = 13.663 A, b = 25.092 A, c = 22.376 A, ~/=90.37~ ). The framework of gottardiite can be described by the interconnection of the polyhedral subunits 5262, 5462 and 54. 5262 and 5462 units have also been found in other zeolites, whereas the unit 54 has been found here for the first time in zeolites. By interconnecting the 5462 and 54 units, a chain is generated which develops along the b axis. These chains are connected to form an impermeable sheet parallel to the ab plane. Each sheet is bonded to other parallel sheets through 4-rings of tetrahedra. The crystal structure is characterized by a two-dimensional channel system. Straight 10-ring channels run parallel to a, whereas 12-ring channels develop along b. These 12-ring channels are interrupted every 25 A (the value of parameter b) by the 4-ring between the sheets, and are connected to the 10-ring parallel to the a axis by a 10-ring window. Therefore these 12-ring channels are not straight, but "snake" in the b direction. 3. TERRANOVAITE The second new natural zeolite found at Mt. Adamson was terranovaite [3]. This mineral is very rare and frequently occurs in globular masses, sometimes in tabular, transparent, bluish crystals, closely associated with heulandite, from which it is barely distinguishable. Yerranovaite [(Na4.zK0.2Mg0.2Ca3.7)tot=8.3(Al12.3Si67.7)tot=80.0O160">29H20]is rich in sodium and calcium and has quite a high Si/A1 ratio (about 5.5). Its topological symmetry, hitherto unknown in either natural or synthetic materials, is orthorhombic, space group C m c m (a = 9.747(1), b = 23.880(2), c=20.068(2)A). However, the presence of a framework oxygen on an inversion center, with an unfavorable T-O-T angle of 180 ~ and the strong anisotropy of some framework oxygen atoms, indicate that the real symmetry is probably described by the acentric sp.gr. C2cm. The framework of terranovaite (Fig. 1), characterized by a pentasil chain, can be described by the interconnection of the polyhedral subunits 4264, 4254 and 5462. The 4264 unit has been found in laumontite and boggsite; the 4254 unit has been found in brewsterite, heulandite group zeolites and in synthetic SSZ-23 and SSZ-33; the 5462 unit has been found in gottardiite, boggsite and in synthetic EU-1. The net of terranovaite projected onto the bc plane (Fig. 1) is equivalent to that of many other pentasil zeolites (ferrierite, boggsite, ZSM5, ZSM-11, theta-1), while the net projected onto the ab plane is equivalent to that of A1PO441 [9]. A two-dimensional channel system parallel to the (010) plane is present in the terranovaite framework. Straight ten-membered ring channels run along [100] and [001]; the former is about circular in section (5.5 x 5.1 A), while the latter is strongly elliptic (7.0 x 4.3 A) (Fig. 1). These channels are connected through a 10-ring window.
86
Fig. 1. Perspective projection of terranovaite framework along [ 100].
4. M U T I N A I T E The third new natural zeolite found in the Ferrar Dolerites of Mt. Adamson is mutinaite [4], the natural counterpart of synthetic ZSM-5. The mineral [(Naz.76K0.11Mg0.21 Ca3.78)(All 1.20Si84.91)O192"60H20] occurs as subspherical aggregates of tiny radiating lath-like fibers or as aggregates of transparent tiny tabular crystals, with good (001) cleavage. This zeolite, very rich in calcium, has a Si/A1 ratio equal to 7.6, the highest found in natural zeolites; however, it is far lower than that of ZSM-5, where this ratio is always greater than 12. Moreover, mutinaite is characterized by a very high thermal stability and a high rehydration capacity. The mineral quickly regains more than 95% of its weight loss at temperatures up to 900~ [4]. The single-crystal structure refinement of mutinaite [ 10] was performed on a microcrystal of 0.03x0.03x0.015mm 3, collecting the data at the beamline ID 11 of the synchrotron radiation source of the European Synchrotron Radiation Facility (ESRF) of Grenoble. The mineral resulted orthorhombic with space group Pnma (a--20.201(2), b-19.991(2), c=13.469(2)A, V=5439 A3). This symmetry is consistent with the high aluminum percentage, and with the content and distribution of the extra-framework species. The structural refinement of mutinaite revealed the absence of order in the Si,AI distribution in the framework; this result is consistent with the conclusions of Toby et al. [ 11 ], who report the absence of highly occupied Br6nsted sites in the high-alumina ZSM-5. When mutinaite is compared with synthetic ZSM-5 phases (with Pnma symmetry) loaded with different molecules, we observe that the mean T-O-T angle is similar: 154 ~ in mutinaite, 155 ~ in TPA-ZSM-5 [12], and 154 ~ in PDCB (p-diclorobenzene-ZSM-5), PNAN (p-nitroaniline-ZSM-5) and NAPH (naphthalene-ZSM-5) [13]. On the contrary, many of the
87 single T-O-T angles of mutinaite strongly differ from the corresponding angles in the synthetic phases (by up to 19~ for T1-O1-T2 of mutinaite with respect to NAPH). These differences mainly affect the shape of the straight ring channel: in mutinaite it is strongly elliptical and, above all, the directions of minimum and maximum elongation are interchanged with respect to those of the synthetic phases.
5. BOGGSITE Boggsite was first described by Howard et al. [14]. This pentasil zeolite occurs in close association with tschernichite in Eocene basalts near Goble, Columbia County (Oregon), and was found for the second time at Mt. Adamson. Boggsite topology [ 15] was hitherto unknown in either natural or synthetic materials. The framework (topological and real symmetry Imma, a=20.25(2), b=23.82(1), c=12.78(1)A) can be described by the interconnection of the polyhedral subunits 4254, 4264, 5462 (found also in terranovaite), 5262 (present with 5462 in gottardiite) and 4262. A straight 12-membered ring channel runs along [100], and a straight 10-ring channel develops in the [010] direction. These channels are connected by a 10-ring window [ 15]. The chemical analyses of boggsite from Goble and Mt.Adamson indicate a constant value of the Si/A1 ratio (about 4.3), which is a usual value for the already known pentasil zeolites, but rather low when compared with that of the other pentasil zeolites from Mt. Adamson. Ca is always the most abundant extraframework cation, whereas Na is rather variable and can reach a content nearly equal to that of Ca. Minor quantities of K and Mg are present.
6. T S C H E R N I C H I T E Tschernichite was structurally defined as the natural counterpart of synthetic zeolite beta [ 16]. At Mr. Adamson the mineral occurs either as large, steep tetragonal dipyramids terminating in a basal pinacoid, or as radiating hemispherical groups of small crystals. Large and small drusy crystals were also reported from Goble tschernichite [17]. Microprobe chemical analyses [1] of large and small tschernichite crystals clearly show that large crystals are richer in A1 than the small ones (Si/A1 ratios 2.66 and 3.94, respectively), as applies also to tschernichite from Goble [17]. Due to the paucity of materials it was not possible to determine the thermal behaviour of tschemichite from Mt. Adamson, but a study on tschernichite from Goble [18] showed that its ammonium form is thermally stable to a temperature as high as 900~ It is known that synthetic zeolite beta can be regarded as a close intergrowth of two distinct, but related, structures [ 19] which can be described as consisting of (001) tetragonal layer-like building units [20]. According to the OD theory, these two structures represent the two maximum degree of order (MDO) topologies. The X-ray powder diffraction pattern of the large crystals of tschernichite-type mineral from Antarctica shows significant discrepancies, mainly in the low 0 region, with respect to those of Goble tschernichite [17] and beta zeolite [19]. These discrepancies, together with the different Si/A1 ratios between large and small crystals of tschernichite,
88
Fig. 2. Projection along [110] of the monoclinic polytype of tschernichite.
suggest that a different ratio of the two polytypes may be present in the crystals of this mineral, depending on their dimensions. We have recently used single crystal X-ray diffraction to study the structure of the two different morphologies of tschemichite from Antarctica, in order to verify if they are characterized by different structural features. Intensity data were collected on a fragment of a large crystal and on a small crystal, using an automatic four-circle Nonius KappaCCD diffractometer equipped with a CCD detector (radiation MoKot). A data collection performed on a large crystal indicated a monoclinic unit cell with a=17.983(3)A, b=17.966(2)A, c=14.625(2)A, [3=114.31(1) ~ V=4306.1A 3 and sp.gr. C2/c. A similar investigation on a small single crystal indicated a tetragonal unit cell with a=12.622(1)A, c=26.674(3)A, V=4249.6A 3 and sp.gr. P4122. The structure refinements of both samples were carried out starting from the DLS atomic coordinates of Higgins et al. [21]. Extraframework sites were located using Fo and AF Fourier maps. The diffraction patterns of both tetragonal- and monoclinic-dominant crystals have in common a set of sharp reflections, with h (and k) = 3n, which are related to the superposition structure. Due to layer stacking disorder, reflections with h (and k) = 3n + 1 show continuous streaks elongated in the c* direction. A detailed structural analysis of each polytype requires a 3-dimensional analysis of the diffuse peaks and an accurate intensity measurement, which can be obtained with an area-detector based diffractometer. For the two tschernichite crystals, the real symmetry was checked with the help of synthetic precession images constructed from the collected flames.
89 Figures 2 and 3 report the projection along [110] and [ 100] of the two polytype structures. The main results of the structure refinements are the following: a) regular T-O distances and partial Si/A1 ordering in both frameworks; b) identification of two Ca sites in the monoclinic structure; c) identification of two Ca sites in comparable positions in the tetragonal structure, but with lower occupancy; d) a further cation site probably occupied by Mg in tetragonaldominant crystals; e) the presence of many other extraframework sites characterized by low electron densities and large distances from the framework oxygens.
Fig. 3. Projection along [ 100] of the tetragonal polytype of tschemichite
90 7. CONCLUSIONS The discovery at Mt. Adamson of so many new and rare high-silica pentasil zeolites, most of which being natural counterparts of synthetic phases largely used in many technological applications, is of great interest as: a) it implies that organic templates, used as directing agents, may not be essential for their synthesis; b) the finding of the natural zeolites discussed above, with a Si/A1 ratio lower than that of the corresponding synthetic phases, suggests that the range of chemical composition required for the crystallization of their structural type is greater than that believed up to now; c) gottardiite, mutinaite and the ammonium form of tschernichite from Goble are stables to temperatures as high as 900~ We can argue that also terranovaite and boggsite are characterized by a similar, very high thermal stability, d) terranovaite and boggsite are interesting additions to the pentasil family, and the synthesis of their analogues should be of great interest to all those who work in the field of microporous materials. All the above described zeolites from Mt. Adamson are characterized by the dispersion of the extraframework ions over a large number of sites; they are usually characterized by weak electronic density and large distances from the framework oxygens which prevent (with the exception of tschernichite) an unambiguous site assignment of cations and water molecules. These features, together with the crystal growth structures of tschernichite, could suggest that these minerals grew very quickly, possibly during a rapid environment cooling, and that they could be metastable at room conditions. The defining of the genetic conditions of these phases, which are potentially useful as molecular sieves and catalysts, is the aim of our future research work. In conclusion, we believe that the results of this research well demonstrate how much natural materials can contribute to the knowledge of microporous materials. To stress this point again, we remind the reader of the recent occurrence of two natural zeolites analogous to previously synthesized phases, and two others lacking their synthetic counterparts: a) gaultite [22], a framework silicate unique in nature with zinc in tetrahedral sites, chemically and structurally analogous to VPI-7; b) pahasapaite [23], a berylloposphate with the same topology as the synthetic aluminosilicate RHO; c) maricopaite [24], an interrupted framework aluminosilicate with lead as dominant extraframework cation, forming Pba(O,OH)4 clusters; and d) tsch[]rnerite [25], characterized by a super-cage with 96 tetrahedra and 50 faces and by CuZ+12(OH)24-bearing clusters. ACKNOWLEDGEMENTS Italian PNRA, CNR and MURST ("Transformations, reactions, ordering in minerals" COFIN 1999) are acknowledged for financial support. REFERENCES
[1] E. Galli, S. Quartieri, G. Vezzalini and A. Alberti, Eur. J. Mineral., 7 (1995) 1029.
91 [2] E. Oalli, S. Quartieri, G. Vezzalini and A. Alberti, Eur. J. Mineral., 8 (1996) 687. [3] E. Galli, S. Quartieri, G. Vezzalini, A. Alberti and M. Franzini, Amer. Mineral., 82 (1997a) 423. [4] E. Galli, G. Vezzalini, S. Quartieri, A. Alberti and M. Franzini, Zeolites, 19 (1997b) 318. [5] A. Alberti and G. Vezzalini, in: Proceeding of the Sixth International Zeolite Conference, D. Olson and A. Bisio (eds.),Butterworth & Co., Guildford, UK, (1984) 834. [6] A. Alberti, G.Vezzalini, E. Galli and S. Quartieri, Eur. J. Mineral., 8 (1996) 69. [7] A. Alberti, in: New developments in zeolite science and technology. Y. Murakami, A. Iijima and J.W. Ward (eds.), Proc. 7 th Int. Zeolite Conf. Kodansha, Tokio, (1986) 437. [8] M.D. Shannon, J.L. Casci, P.A. Cox and S.J. Andrews, Nature, 353 (1991) 417. [9] R.M. Kirchner and J.M. Bennett, Zeolites, 14 (1994) 523. [ 10] G. Vezzalini, S. Quartieri, E. Galli, A. Alberti, G. Cruciani and ,4,. Kvick, Zeolites, 19 (1997) 323. [11] B. Toby, S. Purnell, R. Hu, A. Peters and D.H. Olson, in: Proceeding of the 12th International Zeolite Conference. Treacy, B.K. Marcus, M.E. Bisher and J.B. Higgins (eds.), Materials Research Society, (1999), 2413. [12] H. Van Koningsveld, H. van Bekkum and J.C. Jansen, Acta Cryst., B43 (1987) 127. [13] H. Van Koningsveld, and J.H. Koegler, Microporous Materials, 9 (1997) 71. [14] D.G. Howard, R.W. Tschernich, J.V. Smith and G.L. Klein, Amer. Mineral., 75 (1990) 1200. [15] J.J. Pluth and J.V. Smith, Amer. Mineral., 75 (1990) 501. [16] J.V. Smith, J.J. Pluth, R.C. Boggs and D.G. Howard, J. Chem. Soc., Chem. Commun., (1991) 363. [17] R.C. Boggs, D.G. Howard, J.V. Smith and G.L. Klein, Amer. Mineral., 78 (1993) 822. [18] R. Szostak, K.P. Lillerud and M. St6cker, J. Catal., 148 (1994) 91. [19] J.M. Newsam, M.M.J. Treaty, W.T. Koetsier and C.B. De Gruyter, Proc. Roy. Soc. London, A420 (1988) 375. [20] B. Marler, R. B6hme and H. Gies, in: Proceeding of the 9th International Zeolite Conference, Montreal 1992, R. von Ballmoos, J.B. Higgins and M.M.J. Treacy eds, Butterworth-Heinemann, (1993) 425. [21] J.B. Higgins, R.B. LaPierre, J.L. Schlenker, A.C. Rohrman, J.D. Wood, G.T. Kerr and W.J. Rohrbaugh, Zeolites, 8 (1988) 446. [22] T.S. Ercit and J. Van Velthuizen, Canad. Mineral., 32 (1994) 855. [23] R.C. Rouse, D.R. Peacor and S. Merlino, Amer. Mineral., 74 (1989) 1195. [24] R.C. Rouse and D.R. Peacor, Amer. Mineral., 79 (1994) 175. [25] H. Effenberger, G. Giester, W. Krause and H.J. Bernhardt, Amer. Mineral., 83 (1998) 607.
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Studies in Surface Science and Catalysis 135 A. Galameau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
93
Use of 1H NMR imaging to study the diffusion and co-diffusion of gaseous hydrocarbons in H ~ M - 5 catalysts" P. N'Gokoli-Kekele, M.-A. Springuel-Huet**, J.-L. Bonardet, J.-M. Dereppe, J. Fraissard aLaboratoire S.I.E.N.-Chimie des Surfaces, ESA-CNRS 7069, Universit6 P. et M. Curie, 4 place Jussieu, 75252 PARIS Cedex 05, France bLaboratoire de Chimie-Physique et Cristallographie, Universit6 Catholique de Louvain-laNeuve, 1348 Louvain-la-Neuve, Belgium I H N1V[R imaging has been used to study the diffusion of pure hydrocarbons (benzene, nhexane,) during their adsorption in or desorption from a fixed bed of zeolite crystallites. This technique is used to visualize the progression of the diffusing molecules in the zeolite bed and to determine their intracrystallite diffusion coefficients. In the case of competitive adsorption, it gives the time dependence of the distribution of the two coadsorbed gases.
I. INTRODUCTION NMR imaging (MR/) techniques were developed in the 70s mainly in the medical and biological fields, using essentially the ~H nucleus but also 3He, 19F ,31p, and more recently hyperpolarized 129Xenuclei, etc. The fact that this technique is non-invasive and non-radiative, coupled with the development of more and more powerful equipment and increasingly sophisticated numerical treatment of images, has tended to generalize magnetic resonance imaging in the medical field. However, medicine is not the only field of application of MR/, and the 90s saw considerable progress in this technique for the study of porous media. MR/has been successfully used to study solvent penetration and the dynamics of water in polymers [1,2], the structure and dynamics of polymer gels [3], the segregation of grains in blends [4], the permeation resistance of cement [5], pore size distribution mapping [6] as well as the drying kinetics of gels [7]. It can be also used in microporous systems to investigate the diffusion and molecular mobility of water in 4A zeolites [8] or hydrocarbon diffusion in deactivated Y zeolites [9]. We present here an application of this technique to the study of the diffusion of pure or mixed hydrocarbons (benzene, n-hexane) in a fixed bed of HZSM-5 zeolite during their adsorption at room temperature. In particular, we show for the first time that it is possible to visualize the *The oral presentation in the form of a keynotespeech will also mentionthe studyof diffusion by xenon NMR l~ublishedin this Proceedings to whom correspondenceshouldbe adressed. E-mail: [email protected].~
94 distribution of several gases adsorbed competitively, even if certain results are still essentially qualitative. 2 PRINCIPLE OF THE TECHNIQUE Figure 1 illustrates the principle of the technique. Magnetically equivalent spins in a homogeneous magnetic field B0 (Figure l-a) will give a single signal at a resonance frequency COo,the intensity of which depends only on their number and is independent of their distribution within the sample. However, if a field gradient, g, is superimposed on B0 in the z direction (Figure l-b), the effective field applied to the spins is of the form Bz = B0 + g z; the resonance frequency and the signal intensity depend then on the position and the density, respectively, of the spins at each point z of the sample. More generally, the application of pulsed field gradients during the NMR pulse sequence used for the detection of the resonance signal leads to concentration profiles of resonating spins in the direction(s) of the gradient(s). It is therefore possible to obtain images in one, two or three dimensions. It should be noted that the signal detected depends on the spin density p at each point of the sample but also, depending on the pulse sequence used, on relaxation. For example, in our studies we have used two sequences. In the sequence shown in Figure 2-a, the field gradient is applied during the n/2 pulse and (a) 13o (b) 13o + gz throughout the signal acquisition time, which makes it possible to avoid the problem of spin relaxation and to obtain the real spin concentration profile. In spin echo detection the --+------4 ......... ~-P Z --~-t .... ~ Z Zl 7,2 Z3 Zl Z2 Z3 intensity of the signal depends on relaxation. i i Figure 2-b details, in that case, the periods Acq uisition Acq uisition during which the gradient is applied depending on the pulses used. This sequence can be useful when there is a distribution of the spin relaxation times T2 in the sample, as we have too t~l o~ tt~3 shown in a study of Y zeolite deactivation during catalytic cracking [9] Fig. 1. Prizlciple of 1D NMR Imaging I. EXPERIMENTAL SECTION HZSM-5 zeolite consisting of crystallites, assumed to be spherical, of average radius R = 20 ktrn, was used in the form of a powder or compressed (at 103 bar) into cylindrical pellets 7 mm in diameter and between 5 and 15 mm long, either pure or with a binder (amorphous silica-alumina, SBET ~ 700 m 2 g-l, mean pore diameter 5 nm). Samples placed in the cell (Figure 3) were held under vacuum (10 -5 mbar) at 673 K overnight before the adsorption of gaseous hydrocarbon(s) at constant pressure at 293 K.
95
Fig. 2. Schematic representation of the 1D Imaging NMR sequence: a)Direct acquisition; b) Spin echo acquisition. At time t - 0 the sample is put into contact with the supply of liquid hydrocarbon (n-hexane or benzene) in equilibrium with the gas and is then placed quickly in the magnet. The liquid phase is either pure or consists of a mixture such that the two partial pressures of the gases are equal to 60 mbar (assuming that the mixture obeys Raoult's law). To distinguish the hydrocarbons when they are mixed, one is perhydro and the other perdeutero. The proton 1D NMR images, which represent the concentration profiles of the hydrocarbons along the NMR tube axis are recorded as a function of time with a MSL 300 Bruker spectrometer. They are obtained by applying a magnetic field gradient (Gz ~ 4 T m l) along the direction of the NMR tube axis during which a ~/2 r.f. pulse (RF) is applied and signal acquisition (AQ) is performed (Figure l-a). The length of the sample is small enough (5-15 mm) to permit the application of the excitation pulse during the magnetic gradient.
Fig. 3. Schematic representation of the cell containing the sample.
96 3. RESULTS AND DISCUSSION 3.1 Diffusion of pure gases
The diffusion equations are given by the hydrocarbon mass balance in macropores (eq. 1) and in micropores (eq. 2) [ 10, 11]" t~c c92c 3(1 ~Dintra( tgq] I~inter'~-t -- Dintereinter ~0z2-13inter s R ~ r=R
(1)
cOq ( t 9 2 q , 2 cOq/ cgt = Dint r~ ~ T r 2 "- 7--~r )
(2)
where c and q are the hydrocarbon concentrations in macropores and micropores, respectively; z (linear) and r (radial) coordinates in the bed (from the bottom) and in the crystallite (from the centre); Dinter and Din~ the inter and intracrystallite diffusion coefficients and einter the macroporosity of the sample. These experiments were conducted at pressures where the intercrystaUite diffusion is very rapid with respect to the intracrystallite diffusion. One can verify these conditions from the rectangular concentration profile of the images. In this case only equation 2 is used, with the following boundary conditions: q(r, t=0) = 0;
q(r=R, t) = qoo[1 - exp(-kt)];
aq(r = 0, t) = 0 tgr
where k is the transfer constant of molecules to the external surface of the crystallites, and qoo the hydrocarbon concentration in each crystallite at equilibrium adsorption; then we can use the solution of the diffusion equation (3), obtained by Cranck [ 12],
Mt _ 1- ~ e x p ( - k t ) Moo kR 2
[
1-
cot D intra
+ ~ D intra
)-',
exp
(3)
X2Dintra n = I n 2 (n 2/i;2 - kR 2 / Dintra)
where Mt is the total amount of adsorbed gas at time t (given by the integral of the NMR image signal) and Moo the corresponding value at equilibrium state. It should be pointed out first of all that the hydrocarbon concentration in the gas phase and in the macropores is always negligible compared to that in the micropores (even right at the beginning of adsorption). Consequently, the signal observed is due essentially to adsorption in the micropores.
97 3.1. L Benzene At the very beginning of adsorption, (0 < t < 0.1 h) the 1D images of benzene adsorbing in the powder HZSM-5 bed show a strong concentration gradient decreasing towards the bottom of the sample (Figure 4a). When t > 0.2 h rectangular profiles are obtained for the loose as well as for the compressed powder (Figure 4b) proving that after this time, under these experimental conditions (high pressure of the gas phase) the benzene concentration is the same in any part of the bed and that the diffusion of hydrocarbon is then controlled by the micropores, as discussed by Heink et al. [13]. This allows the determination of Dm~. The results appear to contradict those obtained by NMR of the xenon probe, which demonstrate the influence of intercrystallite diffusion, but in this latter case, the relative benzene pressure is lower a part of the zeolite free volume is already occupied by xenon.. Since compressing the powder increases the density of the sample, the NMR signal is better defined for the compressed sample. The signal intensity increases with the adsorption time. The total amount, M(t), of benzene adsorbed in the sample is directly proportional to the integral of the NMR profiles. The experimental kinetic curves of M(t) = fit) are simulated using equation 3. The simulation gives a Dmt~ value of about 1x 10-14 m 2 s"l whatever the form, powder or pellet, of the sample. This value agrees well with that obtained by 129Xe NMR [14].
a)
b)
Time (h)
~
............. ...... ............ .......... ........... ",---------',--------
Time (h)
15.3
~~
2.4
0.4 0.2
/.- . . . . 9 i. . . .
z=e
z=O
z=e
\_
'7. z=0
9 9
16.00 9.00 4.25 2.25 1.67 1.42 1.17 0.83 0.58 0.25
r--
gas flow
gas flow
Fig. 4. 1D-NMR profiles of adsorbed benzene: a) on powder ; b) on pellet When the sample is the powder zeolite mixed with silica-alumina (60% weight of zeolite, length 25 mm), the benzene concentration profiles (Figure 5-a) present an adsorption front which lasts more than 30 min. On one hand, the intercrystallite diffusion rate is decreased by the presence of the mesoporous silica-alumina, on the other hand benzene also adsorbs on the silicaalumina. In the case of a compressed mixed sample (length 12 mm) the profiles are rectangular as
98 of the first spectrum (Figure 5-b). The difference between the two cases is mainly due to the decrease in the macroporosity and the length of the sample. These results show that mass transport in industrial catalysts depends greatly on the binder, the dimensions and the compression of the sample.
a)
~ t"
Time (h) A
.,~___~
_ 1/'_" --'--'~-~k - - ~ / ~ \ ~ - ----J/ X~--=:=~// \~
b)
~
Time (h)
12.00 s.oo 5.40 4.00
11~
060 .
-J/~,,_--~-~~--
.
0.30 0.25
-~//-~ _J/
~~,~~ ~-~ z=0
z=~
0.20 o.15
-----~/~\~,
.
.
.
;!;; 0.25
0.08 z=e
z=0
gas flow
gas flow
Fig. 5.1D-NMR profiles in a mixture (zeolite/silica-alumina binder) during benzene adsorption: a) powder ; b) pellet 3.1.2. n-Hexane In the case of n-hexane adsorption on a powder sample, the concentration profiles (Figure 6) become perfectly rectangular after only t = 0.03 h. The value obtained for Dm~ (~10 -13 m 2 s -l) is of the same order of magnitude as that reported Time (h) in the literature using other techniques (zero length column, frequency response, etc.) [ 13].
17.80
----37 __--- l:~l __. 0.11 i
0.04
3.2. Diffusion of gas mixtures
Different types of experiments were performed with n-hexane and benzene. Here we report the gas flow results concerning" i) their competitive Fig. 6.1D-NMR profiles of n-hexane adsorbed adsorption, ii) variation of the distribution of a pre-adsorbed hydrocarbon during the in HZSM5 zeolite in powder form. adsorption of a second one. z=~
z=O
99
3.2.L Competitive adsorption. When the adsorption of n-hexane proceeds from a gas phase mixture of n-hexane C6H14and benzene C6D6 both at the same partial pressure, 60 mbar, the intensity of the profiles first decreases from the top to the bottom of the bed (Figure 7-a). Such a profile, which indicates a strong hexane concentration gradient in the sample, persists up to a time of 0.13 h, whereas the adsorption of pure hexane leads very rapidly to rectangular profiles (Figure 6). Several reasons can be proposed to explain this evolution: intercrystallite diffusion slowed, surface barrier lower for n-hexane than for benzene; etc. At intermediate time, there is a slight excess of n-hexane in the bottom of the bed before a homogeneous distribution all over the bed is reached at equilibrium. Whatever the reason, n-hexane adsorbs in the first layers before its pressure becomes equal throughout the bed. The benzene molecules, whose intracrystallite diffusion is much slower than that of n-hexane, progress along the bed and adsorb then on the subsequent layers whose crystallites are free of any adsorbate. As time increases, benzene also adsorbs on the first layers, displacing n-hexane towards the bottom where n-hexane displaces in turn the benzene molecules to finally obtain a distribution governed by thermodynamics. This scenario is confirmed by the evolution of the benzene concentration along the bed, recorded during an identical experiment in which benzene C6H6 and n-hexane C6D14 were used (Figure 7-b). These profiles clearly show that benzene first adsorbs preferentially in the bottom layers before displacing the n-hexane adsorbed in the top layers and finally the equilibrium is reached over the entire sample.
a) Time (h)
~ ~ ~ _ ~
ne (h) 5.88
8.70
4.58
5.08
2.53
4.33
0.83
1.02
0.47
0.57
0.22
0.32 0.25 0.08 0.02
0.13 ~.---__---
0.12
0.07
Z=s
z=O
z= s
z=O Ip
gas flow
gas flow
Fig. 7. 1D-NMR profiles ofn-hexane a) and benzene b) during their competitive adsorption in HZSM-5 zeolite.
100 The intermediate states of the systems are the result of competing kinetic and thermodynamic effects, the diffusion of n-hexane being faster than that of benzene while the latter is more strongly adsorbed inside the crystallite.
3.2.2. Distribution of pre-adsorbate during the adsorption of another gas. Figure 8-a shows the evolution of the distribution of n-hexane C6Hn4 pre-adsorbed at 2 mbar during the adsorption of benzene C6D6 at its saturation vapour pressure. At time t = 0, the concentration profile of pre-adsorbed n-hexane is rectangular. Immediately upon contact with benzene, hexane is seen to be desorbed but preferentially from the upper layers, as is shown in Figure 8-b. However, a practically rectangular concentration profile is obtained rapidly, in about 0.2 h. It should be noted that the amount of hexane desorbed between the beginning of the experiment and the attainment of a new equilibrium is about 40%. Figure 9-a corresponds to the case of benzene C6I-I6 being pre-adsorbed at equilibrium at 6.4 mbar and n-hexane C6Dl4 adsorbing at its saturation pressure. a)
b)
140 ~" 120 me (h)
~
100 80
0
3.90 9.00 ! 9
z =~
[
9
z=0
~
60
20 0 0.17
I
i
0.3
0.47
0.72
z/~
gas flow Fig. 8. a) 1D-NMR profiles of pre-adsorbed C6H14 during C6D6 adsorption, b) Signal intensity versus time for different values of z/g in the bed of the catalyst: II (t - 0 h), [2 (t = 0.02 h), x (t =0.13 h), A(t = 0 . 3 0 h ) , o (t = 1.16h), r (t= 3.90 h ) , * (t= 9.00 h) Time increases from the top to the bottom in figure 8a. We initially observe a rectangular profile corresponding to a uniform distribution of benzene. The total signal area decreases slowly with time. The decrease of the benzene concentration between the beginning and the end of the experiment is about 25 %. But its distribution in the sample is particularly inhomogeneous, as is shown in Figure 9-b. The intensity decreases at the top and increases markedly at the bottom of the bed, showing that the n-hexane adsorbs first in the upper
101 layers, "pushing" the benzene towards the bottom of the tube. The local partial pressure of benzene and, in parallel, its concentration in the bottom of the bed increase.
b~ i o e (h)
-----~~A~,,,
"--~---- 0.02
-~-~~A~"--
- 0.09
60 T ,-':,. gl 50
~4o ,Vo 20
.= -~--'-~ ~ ~ ' - ~
"~-----
-
-'-~~~~'~~----~
-
.-7
i.
.
Z=s
1.51 4.77
.! .~"7 - - - - 1 6 0 6 Z=0
tot 0
0.16
I
I
I
~
0.33
0.5
0.8
0.9
z/~
Fig. 9. a) 1D-NMR profiles of pre-adsorbed C6H6 during C6DI4 adsorption, b) Signal intensity versus time for different values of z/s in the bed of the catalyst. A (t = 0 h), O (t = 0.02 h), II (t = 0. 09 h), [] (t= 0.17 h), O ( t = 0 . 3 1 h ) , x ( t = l . 0 3 h ) , A(t=l.51h), r 9 (t = 16.06 h) Time increases from the top to the bottom in figure 9a. As the "wave" of n-hexane reaches the bottom, this latter gas adsorbs on the lower layers; the two partial pressures become uniform along the sample, and the benzene molecules can adsorb again in the upper layers until the thermodynamic equilibrium is obtained. The distribution of adsorbed gases is first determined by kinetics and then the system is governed by thermodynamics. The difference in the extent of displacement of one gas by another in the two experiments confirms, if this were necessary, the greater affinity of HZSM-5 zeolite for benzene. 4. CONCLUSION The application of ~H 1D-MR/ for the study of hydrocarbon diffusion gives two types of information. First, the variation with time of the surface area of the full signal (amount adsorbed as a function of time) during adsorption makes it possible to determine transport coefficients by simulation of the kinetic curves. For example, the intracrystallite diffusion coefficients of hexane and benzene in HZSM-5 determined by this technique are 10"13 and 10"14 m 2 s"i, respectively, in good agreement with data in the literature. Second, the shape of the instantaneous concentration
102 profiles reflects the variation of the local adsorbate concentration, and reveals a competition between kinetic and thermodynamic effects. In the case of competitive adsorption of several gases, this technique appears to be the only one capable of visualizing the relative distribution of each of the gases in the adsorbate and its variation with time. REFERENCES
1. S. Blackband and P. Mansfield, J. Phys. C: Solid State Phys., 19 (1986) L49. 2. N. Tanaka, S. Matsukawa, H. Kurosu and I. Ando, Polymer, 39 (20) (1998) 4703. 3. I. Ando, H. Kurosu, S. Matsukawa, A. Yamasaki, A. Hotta and N. Tanaka, Wileys Polym. Networks Group Rev., Ser. I (1998) 331. J. Wiley & Sons, Ltd. Publ. 4. P. Porion, N. Sommier and P. Evesque, Europhysics-Letters, 50 (3) (2000) 319. 5. G. Papavassiliou, M. Milia, M. Fardis, R. Rumme, E. Laganas, A. Sepe, R. Blinc, M.M. Pintar J. Am. Ceram. Soc., 76 (1993) 2109. 6. J.H. Strange, J.B.W. Webber and S.D. Schmidt, Magnetic Res. Imaging, 7-8 (1996) 803. 7. I. Koptyug, V.B. Fenelonov, MY. Khitrina, R.Z. Sagdeev and V.N. Parmon, J. Phys. Chem., B, 102 (1998) 3090. 8. M.R. Halse, Magnetic Res. Imaging, 7-8 (1996) 745. 9. J.-L.Bonardet, T. Domeniconi, P. N'Gokoli-Kekele, M.-A. Springuel-Huet and J. Fraissard, Langmuir, 15 (1999) 5836. 10. E. Ruckenstein, A.S. Vaidyanathan and G.R. Youngquist, Chem. Eng. Sci., 26 (1971) 147. 11 L.K. Lee, AIChE. J. 24 (1978) 531 12. J. Cranck, The Mathematics of Diffusion, Clarendon Press, U. K. Oxford, 1956. 13. W. Heink, J. K~ger and H. Pfeifer, Chem. Eng. Sci., 33 (1978) 1019. 14. P. N'Gokoli-Kekele, M.-A. Springuel-Huet, J.-L.Bonardet and J. Fraissard, Proceedings 13th International Zeolite Conference, in press. Elsevier Publ. 2001.
Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
103
Zeolite-based nanocomposites: synthesis, characterization and catalytic applications B.V.Romanovsky Chemistry Department, Moscow State University, Leninskiye Gory, Moscow, 117234, Russia The oxidative in-situ degradation of mono and polynuclear complexes of transition metals within the Y zeolite supercages has been employed to produce an array of oxide nanoclusters encapsulated in the intercrystalline voids of the matrix. The resulting materials were characterized by using a number of experimental techniques. The nanocomposites display extraordinary high activities in oxidation of CO and MeOH. 1. INTRODUCTION Nanocomposites in which one of constituent phases has at least one dimension smaller than 100 nm have recently attracted much attention as perspective functional materials of broad spectrum of applications. The growing interest to these novel systems is quite understandable since the bulk behavior of materials can be dramatically altered by controlling their cluster nanostructures, and this control can lead to greatly improved performance. Besides, the characteristics of nanomaterials could be purposely tuned not only by the variation of the chemical composition of the clusters but also by variation of their size and size distribution. One of the major difficulties in creating the nanosystems lies in the great excess of the surface free energy and as a result in their thermodynamic instability that causes an irreversible aggregation of nanoclusters into larger particles under kinetically favorable conditions. This urged the development of such a research branch as the creation of composite materials in which the nanosized particles are encapsulated in the internal voids of the microporous solids where the cluster size and their interaction to form large aggregates are strongly limited by the steric hindrance Zeolites and zeolite-like materials with their well-organized and regular systems of pores and cavities represent almost ideal matrices to host nanosized particles. The high thermal and chemical stability of zeolite-like matrices would afford the nanocomposites which could operate in a broad range of temperatures and in various media. The zeolite cavities can be considered as peculiar reaction nanovessels where the chemical processes carried out inside them and their products are affected by the confines in which they are being performed. This main principle was proven in mid-70's when the first synthesis of neutral phthalocyanine complexes encapsulated in Y zeolites via intracrystalline assembling was performed at Moscow State University [1,2]. Once formed within the bottle-shaped supercages of Y zeolite, the resulting electroneutral complexes cannon leave them because of spacial restrictions. Later, this new type of inclusion compounds was termed as "ship-in-a-bottle" systems [3].
104 The general strategy for preparing the zeolite-included composites is also based on the ability of restrictive void spaces of the zeolite to control growth of size-confined phases. The in-situ thermal or redox treatments of inorganic or organometallic precursors preloaded into the matrix internal voids yield the metal or oxide particles hosted inside the supercages. The major problems deal usually with the choice of appropriate precursors. Apart from meeting the obvoius geometric criteria, the optimal precursor should also display the substantial solubility in a selected solvent and be stable toward solvolysis or have a substantial vapor pressure and evaporate without essential dissociation or association. The in-situ transformation of the precursor molecules into oxide clusters should be performed under the mildest possible conditions. Otherwise, the elevated temperatures can cause the migration of primarily formed species to the outer surface of a matrix and their aggregation. The present paper reported below is a brief review of our recent advances in the synthesis and investigation of the zeolite-incorporated oxides of some transition metals. 2. PREPARATION OF ZEOLITE-INCORPORATED METAL OXIDES
2.1 Preeursor loading There exist two routes to load the zeolite matrix with metal-containing precursors. First one is the ion exchange of Na for complex cations. In an alternative way, the zeolite is loaded with neutral precursor molecules by utilizing the incipient wetness impregnation technique. Of course, the size requirements for precursor species and the matrix openings are evident to be the key factor in both cases. However, the impregnation technique has some advantages over ion exchange. In fact, the methods for preparing various homo and heterometallic, mono and polynuclear complexes or cluster compounds have been well developed so that the most of requirements to size, shape and solubility of a precursor can be satisfied. This factor becomes crucial when bimetallic oxide clusters should be prepared. Loading the zeolite matrix with discrete precursor molecules containing different metals affords incorporated products with much more predictable and controllable properties than those made via the ion exchange procedure In this respect, the variations of ionic forms of precursors are substantially restricted not to mention some specific limitations imposed on the ion exchange technique. In the present work, we applied a variety of both monometallic and bimetallic complexes to load the zeolite matrix with a precursor. They are listed in Table 1. Table 1 Transition metal complexes used as precursors Monometallic complexes (l.t4-O)L4Cu4C16*, CuPc, NiPc, CoPc, Fe3(CO)12, Fe(acac)3, Ru(acac)3, Zn3(acac)6, Ni3(acac)6, Ag2(FAcO)2**, Cu2(FAcO)4, NiE(FAcO)4, [RuE(AC)4]C1, Fe4(CO)I3(Et4N)2, FesC(CO)I4(Et4N)2, Fe6C(CO)I6(Et4N)2, [Fe30(AcO)6(HEO)a]AcO, [RuaO(AcO)6(H20)3]C104,
Bimetallic complexes Co2Ni2(acac)4(MeO)4(AcO)2, CuNi2(OH)(EtCOO)3(OCH(Me)N(Me)2)2, ReMoOffMeO)7
105 *L = N,N-diethylnicotinamide, **FAcO = CFH2COO- - monofluoracetate anion Of particular interest are two polynuclear precursors: (kt4-O)L4Cu4C16 and ReMoO2(OMe)7 complexes. The first adamantan-like complex has been shown by Davis et al. [4,5] to loose its diethylnicotinamide ligands on contacting the complex in methylene chloride with dry NaY so that only N-free bare (kt4-O)Cu4C16 units enter the zeolite pores. We obtained the similar result with ReMo oxomethoxide complex: after loading it into NaY zeolite since no traces of organic ligands as determined by elemental analysis were found in the sample. So that in this particular case, simple loading the NaY zeolite with these ReMo oxomethoxide complexes results in the ReMo oxide species molecularly dispersed in the matrix bulk. No additional treatment of the metal-loaded zeolite are required to obtain nanomaterial. On the other hand, this very important finding means that the polynuclear core species residing within the zeolite supercages are stabilized by the host framework that plays the role of a peculiar macroligand. Special attention should be paid to the selection of an appropriate solvent. Apart from an obvious requirement of good solubility, the complex precursor used must not dissociate in a selected solvent, e.g., in water. Otherwise, the impregnation may give not only the neutral precursor molecules loaded but also the ion-exchanged species unless the special precautions are taken. As a result, after removing solvent the zeolite cages will contain three types of particles, i.e., precursor molecules, precursor cations and some amount of Na compound. In this case, the outcome of subsequent thermal treatment of the material becomes rather uncontrollable. We faced this situation using the aqueous solution of copper (II) monofluoracetate (see Table 1) to impregnate NaY zeolite. In fact, the starting solid Cu(II) monofluoracetate consists of dimer Cu2(CFH2COO)2 molecules. However, on dissolving in water it gives the monomer species which in turn dissociate into Cu(II) and fluoracetate ions. After impregnation, the resulting sample exhibited some amounts of isolated Cu(II) ions as was evidenced by the characteristic signal of these paramagnetic centers in ESR spectra. This signal remains unchanged even after the treatment of the sample at 400~ in air while the DTA-TG data indicate complete oxidation of the precursor organic part by 250~ [6]. 2.2 Transformation of zeolite-loaded precursors into oxide species With the exception of two very specific cases mentioned above, subsequent in-situ oxidation of loaded precursors is required to convert them into oxide species. It should be kept in mind that by varying the nature of precursor ligands lower oxidation temperatures and therefore better dispersion and lover degree of aggregation can be obtained. As a rule, this procedure can be performed by simple calcination of the material in dry air or oxygen flow at 200-450~ depending on the precursor nature. Oxidation of the loaded precursor to corresponding oxide phase is easily monitored both qualitatively and quantitatively by the DTA-TG technique. In some cases, the GLC analysis of effluent gases can be utilized to control the oxidation of precursors. Another important factor of the oxidation step which must be well controlled during this procedure are eventual losses of the metal precursor compound due to its high volatility. If the rate of oxidation is inadequate, the loaded precursor can sublimate before its oxidation occurs. For example, we found that up to 50% of Zn acetylacetonate as determined by
106 elemental analysis could be lost when the sample with this loaded precursor is heated in a gas flow at about 400~ for 4 hr. 3. C H A R A C T E R I Z A T I O N OF Z E O L I T E - I N C O R P O R A T E D METAL OXIDES Various experimental techniques were employed to characterize the prepared samples. Often, several methods are required to be applied simultaneously to control the consecutive stages of preparation protocol. N__2-BET measurements. These measurements were performed with selected oxidized samples in order to ascertain whether blocking of matrix channels by forming oxide phase takes place. This can be judged on comparing the surface area of starting NaY zeolite with that of the sample after its high-temperature treatment. In fact, a few samples showed about two-fold decrease in surface area which indicates the formation of large particles of oxide phase out of the matrix bulk. X-ray diffraction. Appearance of diffraction peaks consistent with an individual nonzeolitic phase shows unambiguously the formation of oxide particles much more than nanosized [7]. Though the lack of such peaks does not mean the contrary. IR and UV-VIS spectroscopies. The use of IR method enables one to control the loading of precursors and their further transformation into the oxide moiety. At the metal loading as low as a few wt % (metal basis), the IR bands characteristic of metal oxides are too weak to judge on their formation. As to electron absorption spectra, this technique was successfully applied in [8] not only to identify the metal sulfide and solenoid nanoclusters encapsulated in zeolites but also to estimate their mean sizes basing on the blue-shift of absorption-edge in respect to bulk material. Unfortunately, this technique in studying the supported metal oxides turned out to be ineffective mainly because of too broad bands obtained for the samples subjected these investigation. Temperature-programmed reduction by H2. The H2-TPR experiments provide very important information concerning the distribution of metal oxide moiety between the bulk of zeolite support and its external surface. This distinction can be made basing on the positions of peaks in H2-TPR profiles obtained for a sample after the oxidation of loaded precursors and for the corresponding free oxide taken as a standard. For example, NiO/NaY sample gives two H2-TPR peaks centered at 410 and 575~ while bulk NiO exhibits only one reduction maximum at 390~ This result suggests that the hightemperature peak on the first H2-TPR profile could be ascribed to the reduction of intemal NiO species while the low-temperature maximum is very probable to arise from outer nickel oxide. In addition, the measurements of hydrogen uptake in H2-TPR experiments could be used to reveal the valent state of a transition metal present as oxide phase. In the case of Re system, the nominal content of metal was 3.7 wt % with corresponds to 0.74 mmole O/g as Re207 or 0.63 mmole O/g as ReO3. whereas the total amount of H2-TPR consumed between 100 and 1000~ was estimated as 0.72 mmole/g. Measurements of magnetic susceptibility. The zeolite-included oxide clusters obtained from their metallocomplex precursors may in their turn play the role precursor in preparing the materials including nanoscale metal particles. In a few cases of ferromagnetic metals, the measurements of magnetic susceptibility of reduced samples make it possible to establish the distribution of reduced metal between the surface and the bulk of support. Even though the precursor species are at the very beginning evenly distributed, the hightemperature reduction results inevitably in the formation of large metal particles on the
107 external surface of support. Experimental data on the measurements of magnetic susceptibility for a set of Ni containing sample are given in Table 2. On considering these data, it should to be taken into account that the experiments were performed in an apparatus allowing to determine the metal particles sized more than 2 nm, smaller particles are magnetically silent. Given that two-nanometer sized metal particles cannot reside within the zeolite supercages, we measured only the magnetic moiety of reduced nickel on the outer surface of zeolite matrix. It is seen from these results that the share of metal nickel present as small particles less than 2 nm in size decreases dramatically on diminishing the amount of metal loaded. Of course, these estimates correspond also the concentrations of oxide precursors initially hosted in the supercages but only their bottom limit, and the real content of oxide component present as the cage-hosted nanoclusters may be substantially higher. Table 2. Metal contents determined by elemental analysis and by magnetic measurements for nickel-containing samples reduced by H2 at 400~ Total nickel, wt % (EA)
External nickel, wt % (MM)
Internal nickel, %
1.89
0.60
68
1.68
0.91
45
0.81
0.69
15
ESR method. This technique can reveal the changes in coordination and valent state of the paramagnetic ions which may occur during the different treatments of the zeolite with loaded precursor. Also, ESR spectroscopy make it possible to discover any interaction between the paramagnetic centers of different nature when they present simultaneously in a catalyst [9]. Elemental analysis and XPS technique. Joint use of these methods give the important information about the distribution of in-situ formed species between the bulk and the outer surface of zeolite matrix [ 10 4. CATALYSIS BY Z E O L I T E - I N C O R P O R A T E D METAL OXIDES Two model reactions were applied to characterize the catalytic behavior of the zeoliteincorporated metal oxides: carbon monoxide oxidation and methanol conversion. As is clear from what follows, the catalytic activity turned out to be the most sensitive properties toward the minor changes in a catalysts "biography". Therefore, some disagreements may rise on comparing the activity of supposedly similar samples with the same composition but of different preparation history. 4.1 Carbon monoxide oxidation.
This reaction was studied using the zeolite-incorporated CuO catalysts; the samples were prepared employing tetranuclear (I.t4-O)L4Cu4C16 complex as a precursor [7,11]. For comparison, the activity of bulk CuO with surface area of 8.6 m2/g was also evaluated. The
108 process was carried out in a gradientless reactor with the stoichiometric CO+O2 mixture at 450~ and atmospheric pressure. The results are summarized in Table 3. Table 3. Oxidation of CO over the zeolite-incorporated and bulk CuO Cu content, wt % Reaction rate, mole/s.g
2.72
7.52
7.5x 10"2
18.4• 10.2
80 1.94x 10-2
TOF, molecule/s per atom 1.78x 102 1.55• 102 -~ 3• 10 2** * Pure CuO, ** Evaluated basing on the surface concentration of c.a. 1015 atoms Cu/cm 2 As seen, the reaction rates calculated per unit mass of catalyst for the zeolite-based samples are substantially higher than that for the bulk copper oxide regardless many times smaller content of the active phase. Any doubt, the extraordinary high dispersion of CuO explains this difference. In contrast, the TOF values seem to be of the same order of magnitude if one takes into account very approximate evaluation for the surface concentration of Cu atoms. On the other hand, some diminishing in the TOF values on increasing the metal loading suggests that the oxide particles agglomerate probably in neighboring supercages which effect cannot be revealed by any other way. These conclusions are fully supported by the results in which the oxygen storage capacities (OSC) was measured for the samples. The values of OSC were determined by titration of the samples at 450~ with consequent pulses of CO which were introduced into the dry nitrogen flow passing through the sample bed in a quartz reactor till the formation of CO2 ceases. The results obtained in this series of determinations are given in Table 4. Table 4. Oxygen storage capacities of zeolite-incorporated CuO Cu content, wt %
2.72
7.52
OSC, mmol O/g
0.40
1.04
Atomic Cu/O ratio
1.05
1.14
The ratio of copper and reactive oxygen contents which were determined by two independent ways is very close to CuO stoichiometry. This indicates near molecular dispersion of copper oxide moiety incorporated with in the zeolite matrix. 4.2. Methanol oxidation The reaction was carried out in a fixed-bed quartz reactor at 90-400~ The reaction products were analyzed by a GLC technique. Carbon dioxide and formaldehyde were found to be the only products of methanol oxidation; in no case the formation of CO was detected. In parallel to oxidation, the dehydration of methyl alcohol also occurs, dimethyl ether (DME) being a product. Fig.1 shows the results obtained with the Fe containing sample prepared using hexacarbonyl triiron (see Table 1) as a precursor. Similarly to the case of CO oxidation, TOF values for methanol oxidation are noticeably dependent of the total metal loading. This also could be due to the intracrystalline agglomeration of iron oxide nanoparticles that
109 decreases the efficiency of Fe active centers because of the changes of their mean coordination to oxygen atoms. An alternative explanation for these findings would be suggested such as influence of diffusion limitations inside the matrix micropores. In fact, a non-linear dependence of the measured reaction rates on active component concentrations is to be expected, provided the diffusion limitations would play a significant role (see $2 histogram series in Fig.l). However, this effect seems to be little possible since the difference in the measured values of reaction rates for CO and MeOH oxidation amounts to two order of magnitude which makes the Thiele modulus to vary ten times. This latter excludes the diffusion effects from consideration. On the other hand, the results of catalytic measurements could discover the effect of steric non-compatibility of precursor molecules and matrix pore openings that makes it impossible to load the matrix with a precursor compound. In Table 5, the total conversions of MeOH are compared for a set of iron-containing samples with about 1 wt % Fe prepared by utilizing the iron carbonyl complexes of various nuclearity - from 3 to 6 (see Table 1). In contrast to four-nuclear Cu and ReMo complexes that can readily loose their labile ligands before entering the zeolite channels as mentioned in the previous section, polynuclear Fe cluster compounds are too rigid and cannot penetrate the matrix pores unless the molecular size allows this. Table 5. Total methanol conversion over zeolite-incorporated Fe oxide Sample
NaY
Fe3/NaY
Fea/NaY
Fes/NaY
Fe6/NaY
Methanol conversion, %
11.7
54.1
2.6
2.2
2.9
NaY starting material, Fe3, Fe4, Fe5 and Fe6 - samples obtained from tri, tetra, penta and hexanuclear iron carbonyl complexes, respectively; reaction temperature - 400~ -
As seen from these data, the loading of parent NaY zeolite with iron oxide via trinuclear Fe carbonyl as a precursor increases greatly the total rate of methanol conversion because of the appearance of oxidative active centers. In contrast, the use of carbonyl complexes of four and more nuclearity resulted in a dramatic drop of MeOH conversion even in comparison to the starting material. It should be noted that all Fe-containing samples have the same amount of iron oxide (about 1 wt %, metal basis), and such an effect can be explained only on assuming the formation of multilayer oxide deposits that cover the outer zeolite surface including its pore mouths. This assumption was verified by measuring the surface area for this set of samples that decreases from about 700 m2/g for NaY down to a few tens m2/g for three last samples in Table 5. It should be added that these findings seem to be significant in one more respect. They allow to make some conclusions, though indirect, concerning the behavior of complex molecules other than iron ones as precursors upon reaction with microporous matrices like NaY material. In fact, the large complexes such as CuNi2(OH)(EtCOO)3(OCH(Me)N(Me)2)2 and C02Ni2(acac)a(MeO)n(AcO)2 are evident to be impossible to penetrate the Y zeolite channels of 0.7 nm in diameter. Nevertheless, the impregnation of NaY zeolite with acetonitrile solutions of these complexes yielded about 1% loading (metal basis) with a negligible decrease in the surface area. Even though there were no analytical measurements for organic residues in the samples prepared by such a
110 route, these multiligand polynuclear complexes could be expected to behave in a very similar way that analogous ReMoO2(OMe)7 and (kta-O)LaCu4C16 complexes do. As depicted previously, on contacting with parent NaY material, namely they loose their organic ligands stabilizing the polynuclear metal core and change them for an inorganic environment on residing within the supercages. Of course, this conclusion can by no means be generalized so that every particular case of a metallocomplex with polynuclear core as a potential precursor to be loaded into a micropore matrix required the special investigation. It would be of interest to compare the zeolite-based oxide catalysts prepared by loading the parent material with polynuclear metallocomplex precursors with those obtained via traditional impregnation with a metal salt. In Table 6, the experimental results on methanol oxidation we obtained for a series of Co and Ni containing samples are summarized. Although the samples (except for the first one) contains the same amounts of loaded metal oxide, the efficiency of those obtained via polynuclear precursors differs dramatically from that for the conventional zeolite-supported NiO. These data are well consistent with the results found for CO oxidation that was carried out over the analogous set of catalysts. Table 6. Methanol conversion over the zeolite-incorporated Co and Ni oxides Catalyst Metal, wt % Temperature, ~ Reaction time, min Conversion,% Selectivity b, % carbon dioxide dimethylester
Co2Ni2/NaY Co4/NaY 0.5 1 250 250 82 122 163 80 120 142 85 83 88 91 93 94 99 98 99 1 2 tr.
98 99 97 2 1 3
Ni4/NaY 1 250 84 131 242 73 79 72
Ni/NaY 1 350 60 120 5 4
98 99 97 2 1 3
3 4 97 96
Note: Co2Ni2/NaY, Co4/NaY and Ni4/NaY samples were obtained via four-nuclear complexes (see Table 1), Ni/NaY sample was prepared by the impregnation of parent NaY material with aqueous solution of Ni nitrate Lastly, the comparison of activities determined for monometallic and bimetallic oxide catalysts can provide an important information on whether two oxide components are independent active entities or they can interact with each other. This was illustrated by Fig.2 where the TOF values for monometallic Ru (S 1series) and Fe ($3 series) samples and bimetallic RuFe ($2 series) samples are depicted. It should be noted that in the mixed RuFe samples ruthenium and iron concentrations are close to their content in corresponding monometallic analogs. As seen, the activity of Fe-containing samples is significantly smaller than that of Ru-containing catalysts. From this result, the activities of mixed RuFe samples would be expected to be similar to those for Ru catalyst set provided the additive effect is operative. However, it is not the case, and the activity of ruthenium centers becomes inhibited in the presence of iron species. Such non-additive effect could be due to the chemical interaction of oxides which occurs within the nanosized internal voids of zeolite matrix and is enhanced by severe spatial restrictions. Similar effects we have observed [9] for Fe-containing Y zeolite. Upon loading this zeolite with Cu(II) acetate
111 complex, the Fe(III) centers becomes fully ESR silent because of interaction of neighboring paramagnetic atoms. The examination of zeolites modified with transition metals as catalysts of methanol conversion have revealed the close connection of redox and acid-base functions of these catalytic systems. In fact, methyl alcohol can react by two pathways that are supposed to be rather independent. The acid centers of zeolites are commonly believed to be responsible for dehydration of methanol to dimethyl ether while the oxidative sites account for the formation
Fig. 1. Activity in MeOH oxidation of Y zeoliteincluded iron(Ill) oxide: 1-0.18 wt% Fe; 2-0.39 wt% Fe; 3-0.76 wt%Fe. S 1 - TOF values, a.u. $2 - activity per unit mass
Fig.2. Activity in MeOH oxidation of Y zeoliteincluded ruthenium (S 1), rutheniun-iron ($2) and iron ($3) oxides per unit mass of metal as the function of Ru (1-4), RuFe (5,6) and Fe (7-9) loading
of formaldehyde and carbon oxides. In this connection, we have investigated more closely the simultaneous occurrence of both reactions using the zeolite-incorporated oxide catalysts [12]. The catalysts was obtained by oxidative degradation of Cu, Ni and Co phthalocyanine molecules (see Table 1) that were previously "ship-in-bottled" into NaY zeolite. Methanol conversion was performed in air or in nitrogen flow. Below 250-280~ the yields of dimethyl ether in air were found to be noticeably higher than in nitrogen. These somewhat unexpected results were explained by assuming the dual-site mechanism
112 of methanol dehydration. It was suggested that the transition state includes both basic and acid sites that further gives DME. Besides, the basic center can react with MeOH molecule yielding carbenoid-like surface intermediate. These intermediates are more or less stable in an inert media and thereby break the well-organized structure of dual sites which make it impossible to form the transition state of dehydration pathway. On the contrary, the carbenoid species are readily oxidized in air and this restores the active sites accounted for methanol dehydration. 4. CONCLUSIONS Faujasite-type zeolites with the bottle-shaped supercages are the most suitable matrices that provide good opportunities for preparation of the nanocomposite materials using mono and polynuclear metal complexes with organic ligands as precursors. The spatiallyhindered in-situ oxidation of these precursors preloaded into the cages yields the highly ordered systems of oxide nanoclusters. The migration of these clusters is strongly retarded within the matrix micropores so that their aggregation to form large particles on the outer surface is little probable. The highly dispersed oxides incorporated into the zeolite intracrystalline voids exhibits good catalytic performance in carbon monoxide and methanol oxidation. ACKNOWLEDGEMENT
This work was financially supported by Grant 99-03-3298 and Grant 00-15-97346 from the Russian Foundation for Basic Research. REFERENCES
Romanovsky B.V., Zakharov V.Yu., Borisenkova S.A., USSR Patent, No.552752, 1975. Zakharov V.Yu., Romanovsky B.V., Bull. Mosc. State Univ., Ser 2, 18 (1977) 142. Herron N., Stucky G.D., Tolman C.A., Inorg. Chim. Acta, 100 (1985) 135. Abdel-Fattah T.M., Davies G., In: Multifunctional Mesoporous Inorganic Solids (C.A.C.Sequeira and M.J.Hudson, Eds.,), Kluwet Acad. Publ., 1993, p. 121. 5. Davies G., Giessen B.C., Shao L., Mater. Lett., 9 (1990) 231 6. Boltalin A.I., Knyazeva E.E., Zhilinskaya E.A., Aboukais A., Russian J. Phys. Chem., 75 (2001) 231. 7. Abdel-Fattah T.M., Davies G., Romanovsky B.V., Shakhnovskaya O.L., Larin A.M., Jansen S.A., Palmieri M.J., Catal. Today, 89 (1996) 1121. 8. Tolkachev N.N., Stacheev A.Yu., Kustov L.M. Abstr. Internat. Boreskov Memorial Conf., 2nd, "Catalysis on the Eve of XXI Century", Novosibirsk, 1997, p.256. 9. Boltalin A.I., Knyazeva E.E., Zhilinskaya E.A., Aboukais A., Bull Mosc. State Univ., Ser 2, Chem., 41 (2000) 293. 10.Romanovsky B.V., Gabrielov A.G., Mendeleev Commun., 1 (1991) 14. 11.Berdanova E.I., Larin A.M., Shakhnovskaya O.L., Romanovsky B.V., Bull. of Russian Acad. Sci., Ser.2, Chem., (1997) 1761. 12.Kustov A.L., Moskovskaya I.F.,Romanovsky B.V., Zhilinskaya E.A., Aboukais A., Recent Reports at the lntern. Congr. on Catal., 12th, Granada, 2000.
1. 2. 3. 4.
Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
113
Application of Combinatorial Tools to the Discovery and Commercialization of Microporous Solids: Facts and Fiction Jennifer Holmgren, a David Bem, a Maureen Bricker, a Ralph Gillespie, a Gregory Lewis, a Duncan Akporiaye, b Ivar Dahl, b Arne Karlsson, b Martin Plassen, b Rune Wendelbo b a UOP LLC, 25 East Algonquin Rd., Des Plaines, Illinois, 60017, USA b SINTEF, P.O. Box 124, Blindern, 0314 Oslo, Norway
During the past three years, combinatorial tools and methods have received increasing amounts of attention as potentially enabling methodologies for the chemical industry. We have developed a combinatorial multiautoclave, which can be used to explore hydrothermal space efficiently and effectively. Our recent results illustrate the applicability of this capability to both the discovery and scale-up of microporous solids. 1. INTRODUCTION The chemical industry faces an extremely competitive business climate. In addition, innovation in this industry has slowed as catalyst and process technology has matured. 1 Despite the maturity of the catalyst industry, there is a continuing and growing need for improvements in catalyst performance, to increase the efficiency of industrial processes and reduce their environmental impact. Such increases cannot be obtained through incremental improvements using existing development methodologies. In order for the chemical industry to maintain a competitive advantage, a breakthrough in catalyst R&D methodologies is greatly needed. The pharmaceutical industry faced similar circumstances in the 1980s as the high cost of drug discovery became incompatible with downward pressure on drug prices. In that case, combinatorial chemistry, with high throughput screening and integrated informatics, provided a breakthrough methodology for the pharmaceutical industry to increase its innovation ability. We believe that the successful application of combinatorial methods to the chemical industry could have similar benefits: 1) an increase in the rate of catalyst innovation and 2) a decrease in commercialization cycle times. Because of this belief, UOP and SINTEF have developed their End-to-End T M combinatorial catalyst discovery system. This system includes the ability to perform all the critical catalyst processing operations combinatorially (Figure 1). We have validated each of these steps using commercially relevant catalyst examples. In addition, we have utilized the entire system to prepare and test catalysts for catalytic applications.
114
Figure 1. Unit operations in our End-to-End SMcombinatorial catalyst discovery system. An essential element of extending combinatorial methods to catalysis is the ability to synthesize libraries of inorganic materials. 2'3'4'5 Workers at SINTEF were the first to report the successful development and implementation of a combinatorial hydrothermal synthesis cell. This cell lies at the heart of our library preparation system. 2 Other workers have also reported methods to synthesize libraries of materials from hydrothermal reaction. 3'4 The successful implementation of a miniaturized hydrothermal multiautoclave requires dealing with a number of technical hurdles: 9 9 9 9 9 9
synthesis
Demanding experimental conditions related to high pressure and high temperature Chemically aggressive conditions such as high pH and HF High sensitivity to preparative procedures Complex heterogeneous systems including gel formation and phase separation Labour intensive work-up procedures, and Complex characterization
Our multiautoclave addresses the problems of parallel syntheses, parallel work-up and rapid screening and offeres a new tool for efficiently charting a variety of chemistries. Using this multiautoclave as its foundation, we have created an integrated, fully automated hydrothermal synthesis system, which includes the following fully integrated capabilities: 9 9 9 9 9
Statistical experimental design with chemical constraints Reagent transfer Data logging of all relevant process conditions Parallel work-up and isolation Automated X-ray and SEM analysis
115 We have successfully utilized our integrated system to synthesize and characterize zeolites, A1POs, microporous oxides and other relevant inorganic oxides. We find that although we are working with microliters of reagents, that the results in this multiautoclave are scalable to the laboratory scale (125 ml). In terms of applicability, we have utilized this system for the discovery, optimization, and the scale-up of new materials. We will present four examples throughout this paper to demonstrate this capability. 2. EXPERIMENTAL To illustrate the experimental procedures used, details regarding the experimental work for a Zn-Cu-V-O example are presented here. The compositional variables, reagents, and digestion parameters used for the Zn-Cu-V-O combinatorial experiment are given in Table 1. The aqueous reagents were delivered to a multiautoclave via a robotic pipetter with concurrent agitation of the reaction mixtures. After sufficient homogenization, the multiautoclaves were sealed and digested at the appropriate conditions. After the digestion, the samples were washed, pulverized, isolated and mounted for powder X-ray analysis. The recovery process was completed using parallel methods. X-ray diffraction data were collected on a Bruker AXS D8 powder diffractometer. The diffractograms were then analyzed using automated data handling methods. Table 1 Variables and Their Values in the Vanadate Combinatorial Experiment
Variable
Multiplicity
Zn-Cu Mixture (Zn + Cu)/V Ratio OH-/V H20/V Replicate Standards Temperature Time Reagents Total Experiments
5 2 4 1 8 3 2
Values ZnxCUl_x, x = 0, 0.25, 0.5, 0.75, 1.0 (Znx + Cul.x)/V = 1or 2; x as above 0, 0.33, 0.67, 1.0 200 Zn:V:OH:H20=2:l :0.33:200 100 ~ 150 ~ 200 ~ 38hr, 168hr Zn(NO3)2*25 H20, Cu(NO3)2*25 H20, H20, NaOH*5 H20, and Na3VO4*60 H20 288
3. RESULTS AND DISCUSSION In a conventional investigation, one often will prepare a homogenous reaction mixture, split the reaction mixture among several autoclaves, and digest these autoclaves for a variety of temperatures and times. Essentially, the conventional experiment explores digestion conditions for a specific synthesis gel. A combinatorial or multiautoclave experiment, on the other hand, is designed to study a variation of compositions across the multiautoclave assembly. The digestion study can be performed by preparing a series of multiautoclaves with a set of gel compositions and digesting each multiautoclave at a different condition. By using a specific multiautoclave assembly to explore gel composition space and a series of multiautoclaves to study digestion conditions, composition space can be mapped very efficiently.
116 K20 0.0
1.0
02/ . \o8 _" ~ \o~ 04/ , \o~ ~ .\o~ ~ ~o~ ~ 9 \o~ ~ , 9 \o~ ~ , \Ol
K20 Original Design Combinatorial Design__
~.o / . . . . . ," \ o.o TEA20 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 Na20
~176 o.y'\og
0 .u~v ~ u.i8: 0 ~, " .8.7
o.~:',,\ .* ,,, \06
0~/,.,
~ ..'~o~ ~ V;,~4 0~--~~ : \0.3 0 ~ - , ; , , . \0.2 1.0# - v v v v v - ~" v ; ~ . ~" TEA20 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0"0Na20
Figure 2. Exploration of the xTEA20: yNa20: zK20: A1203:10 SiO2:150 H20 (x+y+z=3) system. The first phase diagram illustrates the experiments done in the conventional design of experiments (DOE); the second shows the experiments performed using the combinatorial approach.
3.1 Combinatorial Investigation of Al-Si-O Systems Figure 2 shows two phase diagrams. These represent the exploratory investigation of a zeolitic synthesis space at a 10:1 SIO2/A1203. In this experiment, the impact of varying the K20:Na20:(TEA)20 ratio was examined. The original experiment, done using conventional methods, explored 10 compositions while the combinatorial experiment explored 100 compositions. In order to validate that the multiautoclave effectively mimics the laboratory scale, the combinatorial experiment also included the 10 original gel compositions. In all cases, the laboratory results were reproduced. In addition, because oxide synthesis and crystallization is intrinsically an inhomogeneous process, to ensure reproducibility on the scale of the combinatorial experiment, replicates were used within and between the multiautoclaves. In all cases the experimental results were consistent with expectations. In this example, the work done to explore the original 10 compositions required approximately one man-month of labor during an elapsed time of six months. The combinatorial experiment, on the other hand, was done over a one-week period utilizing only two days of labor. In addition to the tremendous increase in productivity demonstrated here, the experiment also illustrates that the combinatorial approach can more effectively cover the entire reaction space. Because these synthesis systems are inherently discontinuous, a broader exploration will likely result in increased knowledge and a decreased probability of missing a critical result. The previous example illustrates the use of combinatorial methods to explore novel reaction space. This next example will illustrate the use of combinatorial methods to focus on the details and reexamine a "known" system: mixed alkali structure direction in the Si/A1 = 3 and 10 systems. The experiment consisted of 15 high symmetry alkali combinations of Li § Na +, K § and Cs § including four 1-way interactions, six 2-way interactions, four 3-way interactions, and a 4-way interaction. This design is shown in Figure 3. Including replicated reactions run for quality control, 960 reactions were run. This work is described in depth in the paper presented by Lewis at this conference. 6
117
Na Li
9 Single 4-way interaction 9 3-way interaction + 2-way interaction 9
K
Cs
mmm
Temp 125~
150~
Figure 3. Experimental design for alkali template combinations investigated displayed on a tetrahedral quaternary phase diagram, along with reaction stoichiometries and process conditions. The high-symmetry points selected to cover the experimental space include the four individual templates (o), the six 2-way combinations (+), the four 3-way combinations (A), and the one 4-way combination (m), yielding 15 unique alkali template combinations. This study mapped out the compositions and conditions leading to the major pure products, including BEA, ANA, MER, LTL, and pollucite (ANA-Cs). An assumption in this experiment, that TEA + would do little structure direction at Si/A1 = 3, proved valid as BEA was only observed at Si/A1 = 10. Pollucite, the Cs analog of analcime (ANA-Cs), was the only other major pure product observed at Si/AI = 10, forming at the higher hydroxide levels of OH-/(Si+A1) = 0.55 and 0.64, while BEA formed at 0.45 and 0.55. Cs + was the strongest structure director among the alkali at Si/A1 = 10; BEA did not form if the Cs level exceeded 0.67 Cs/A1. The low ratio materials LTL and ANA were also observed on several occasions at Si/A1 = 10, but only at the highest hydroxide level of OH/(Si+A1) = 0.64. Presumably the hydroxide concentration was high enough to dissolve sufficient silica to allow the lower ratio materials to form. Such a study can be easily done in a month's time using combinatorial methods and illustrates the value of the combinatorial tool in mapping compositional space. In addition, this experiment illustrates the difficulty in designing the experiment such that the key interactions of the variables can be understood in a minimum number of experiments.
3.2 Combinatorial Investigation of the Zn-Cu-V-O System The use of the multiautoclave assembly is not limited to the exploration of zeolitic synthesis gels. A study was carried out in the Cu-Zn-V-O system, a system that we had previously examined as part of an effort to prepare novel metal oxides. This study resulted in an increase in fundamental knowledge of a well-known system due to the increased density of the information collected using combinatorial methods. The conventional study yielded the material Zn3V2OT(OH)2*2H20, the structure of which was solved by ab initio methods on powder x-ray diffraction data. 7 The hexagonal structure consists of LDH- or brucite-like Zn oxyhydroxide layers separated by pyrovanadate groups. Since a similar monoclinic structure was known for the Cu analog, the mineral volborthite s, we explored the Zn-Cu mixed metal system. This study resulted in a new structure that was prepared at high temperature having
118 the stoichiometry CuZnVO4OH. 9 The LDH-like Zn and Cu layers are buckled in this structure giving rise to a more dense structure containing orthovanadate groups and 5-coordinate Cu and Zn between the layers. The structural evolution of the reaction composition given by Zn : Cu : V : H20 of 1.5 : 0.5 : 1 : 200 in temperature and time is shown in Figure 4. The crystallinity of the Zn3V207(OH)2*2H20 phase increases with time at 100 ~ and 150 ~ while conversion to the CuZnVOaOH-type structure is observed at 200 ~ An examination of the replicate composition as the Zn is systematically replaced by Cu, is shown in Figure 5. The figure clearly shows the hexagonal pattern associated with the Zn-rich compositions converting to an intermediate species when equal amounts of Zn and Cu are present. Further addition of Cu yields the more complicated monoclinic pattern associated with volborthite, Cu3V207(OH)2*2H20. These three structures were the dominant products in the 100 ~ and 150 ~ chemistry.
1250'
j/k
A200oc,
~
; :
;jr ~
i t.j
:,i ~ ,
li' i il i .:, ~1 ! ~ 150~
7d
2~o_ ~
i
!./ \
:~
! !
]/I
i ^ IA150~ ,
2d
i'
I'' t
I
I'
2d
I
'
i "~-
I 0
'
5
10
'
15
20
2-Theta(*)
'
25
30
!
100~
I
35
Figure 4. The structural evolution of the reaction composition given by 1.5 Zn: 0.5 Cu: 1.0 V: 200 H20 in temperature and time. There were several other interesting products observed at 100 ~ and 150 ~ over the course of this study. The layered intermediate Cu2(OH)3NO3 was observed in a number of preparations that usually included the higher levels of NaOH. Zn-containing analogs were also observed. These products were observed only after 38 hr; by 168 hr they were always converted to volborthite or one of the similar Zn-containing phases. The Cu2(OH)3NO3 structure has a similar LDH or brucite-like structure observed in the layers of volborthite and Zn3V207(OH)2*2H20. ]~ This intermediate had never been observed in the original conventional study, probably due to the fact that acetates rather than nitrates had been employed. It is not apparent whether these hydroxynitrates are precursors or just less stable competing phases.
119 Another material in this category had an unidentified x-ray diffraction pattern and was the major product in 11 of the reactions, often forming along with volborthite. A single formulation, Cu : V : O H : H20 of 1 : 1 : 0.33 : 200 digested at 150 ~ for 168 hr gave a pure material. This formulation was scaled up in a 125 ml autoclave. A comparison of the diffraction patterns from the combinatorial experiment and the scale-up show excellent agreement. Further characterization by elemental, thermal analysis and SEM showed this material to be a new copper vanadium oxyhydroxide with the empirical formula CUllVa(OH)8017 and a needle-like morphology. 1500
Cu3V207(OH)2
Monoclinic
0
1000
0.5
t.o r-o
1
ce--
500
-
1.5
=2 0
5
lO
15
20
2-Theta(*)
2~
3o
35
Figure 5. Impact of systematically replacing the Zn by Cu [(Znx Cu2_x)/V=2, OH-/V=0.33]. Phase transition from hexagonal to monoclinic observed with increased Cu incorporation. These data illustrate the value of combinatorial methods to elucidate fine details of the synthetic chemistry. We believe this is one of the key features of using a combinatorial experiment - the ability to carefully define the phase space of interest and develop a deep understanding of the chemistry. In addition, even in a well-studied system like this one, new materials were uncovered that had been missed in the previous conventional work.
3.3 Combinatorial Investigation of M-AI-P-O Systems As a final example, the preparation and characterization of a series of metalloaluminophosphates was performed by screening a diverse mixture of gels based on variation of the chemistry of the inorganic and organic components. This involved the introduction of cobalt, magnesium or silicon into gels formed using cyclohexylamine, cyclopentylamine, N-methylcyclohexylamine and 4-methylcyclohexylamine as the organic structure directing agents. A total of 200 gel mixtures were prepared, including a series of
120 selected replicates and controls to probe the reproducibility of the experimental procedures across the parallel format. Crystallization of the gels was carried out for 24 h at 200 ~ followed by parallel filtering and washing stages. A set of eight identical gel compositions all generating a major AFI phase, randomly distributed within and between plates, confirmed the level of reproducibility achievable across the parallel format, even at this miniaturized scale.
Figure 6. Distribution of the AFI (dark) and CHA phases obtained in the A1POsyntheses. Labelling defined as follows: CH = cyclohexylamine, CP = cylcopentylamine, NCH = N-methylcyclohexylamine, MCH = 4-methylcyclohexylamine. The inorganic composition is defined according to: A = aluminophosphate, AX = metalloaluminophosphate composition (e.g. ASi = SAPO). Within the compositions studied, two of the major known phases identified were the AFI and CHA topologies. A correlation of these two phases as a function of synthetic parameters has been analyzed, and is summarized in Figure 6. Under the conditions presented here, many of the products were, not surprisingly, dominated by the presence of the AFI phase. However, in the presence of cyclohexylamine and cyclopentylamine pure CHA phases were obtained. To our knowledge, the formation of a pure SAPO-34 in the presence of cyclopentylamine has not been reported previously. This example again serves to illustrate the value of using combinatorial methods to fully characterize well-known systems. New information and knowledge can be collected even when exploring well-known/characterized systems. 3.4 Combinatorial Chemistry as a Scale-up Tool
Materials manufacturing can also benefit from combinatorial methods. Libraries to optimize recipes and process conditions can be studied using many of the methods and assays developed for materials discovery. The ability to correlate the synthesis variables with materials properties is valuable in determining manufacturing specifications for a given
121 material and ensuring the robustness of its synthesis. These tools and the resulting information will decrease the cost of manufacturing development and speed delivery of new materials to market. We have demonstrated the applicability of combinatorial methods to accelerate the scale-up and commercialization of new materials. In a recent example, we worked on the scale-up of a novel zirconium silicate. ~2'~3 These proprietary materials have demonstrated excellent selectivity for ammonium cations and as such could be important ion exchange materials in medical applications. 14 To accelerate commercialization of these new materials, we used combinatorial methods to determine the most robust composition region for their synthesis. A relevant subset of the 144 distinct compositions that were prepared is shown in Figure 7. In this work, the impact of gel composition on the formation of two distinct zirconium silicate phases was studied: "Product 1" and "Product 2." In this particular case, "Product 1" was the desired product. In the experiment, the Na, Zr, water and seed levels were varied. The initial laboratory scale work was performed in the left upper quadrant: high water, low Na, low Zr, no seed. Note that in this region small changes in any of the parameters results in formation of "Product 2" and amorphous material. The combi experiment uncovered a more robust region: the right, lower quadrant. In this region, the desired product could be synthesized over a wide range of Na, Zr, and water levels. This region is more robust: formation of "Product 1" is relatively insensitive to synthesis conditions. Such a robust recipe can be transferred more quickly to manufacturing. This optimization work was done in a two-week period and resulted in a significant reduction of the commercialization timeline for this product. Low Na
High Na
9 9 9 9 9 ..~
9
m
9
9 Am
Low Na 1
1
I
H i g h Na 1
1
9 9 9 9 9 9 9
9
9
9
Low Na iI
9
9
[ 1
1
I,~
m
i II II ii
I
/
9 m m j .. .~ 9 lm
II IN
o .d
m
9
9
9
9
9 9
9 9
9 9
9 9
9 9
9 9
9
9
9
9
9
9
9
9
9
9
Iml
9 9
9 mm"mm
Product #1" 9 Product #2: Wk Amorphous: l
9
High Zr
Low Zr 9
High Zr
'.k ..
t t
Seed 2
Low Zr
9 mm-A mm 9- 9 ._.
I I
No Seed
9
J ,j .
I I
IroN IroN ImI Iml 9
9
]
IN 9
H i g h Na /
Seed
1
Identified Robust Region for Product 1
Figure 7. Combinatorial optimization study of a zirconium silicate synthesis. This data was used to accelerate the scale-up and commercialization of a new material.
122 4. S U M M A R Y
We have successfully applied combinatorial synthesis methods to 1) discover and 2) scale-up inorganic oxides. We find that the tighter control of reaction conditions, coupled with the ability to systematically vary gel composition, enables a broader exploration and results in an increase in the fundamental understanding of the space being studied. The suggestion that combinatorial methods are a degeneration of the scientific process to a "monkey approach" is inconsistent with our experience. In fact, we find that combinatorial chemistry presents a greater challenge in experimental design and can be used equally well for the gathering of fundamental information as for the discovery of new materials. Furthermore, the fully computer controlled system with online monitoring of every step in the process ensures quality control and reproducibility. Unfortunately, it is difficult to distinguish between truth and fiction at such an early stage in the implementation of combinatorial tools to heterogeneous catalyst processes. In the next few years, we will learn the value and limitations of the combinatorial tool through exposure and use of this new methodology. Our experience to date, however, does suggest that the possibilities for the application of combinatorial tools in the chemical industry are exciting. We look forward to the challenges and opportunities that this will present. REFERENCES
1. W. Rothwell, C. Shearer and G. Taylor, Chemtech, 1995, 25 (6), 6. 2. D. E. Akporiaye, I. M. Dahl, A. Karlsson and R. Wendelbo, Angew. Chem., Int. Ed., 1998, 37 (5), 609. 3. K. Choi, D. Gardner, N. Hilbrandt and T. Bein, Angew. Chem., Int. Ed., 1999, 38 (19), 2891. 4. J. Klein, C. W. Lehmann, H-W. Schmidt and W. F. Maier, Angew. Chem., Int. Ed., 1998, 37 (24), 3369. 5. E. Danielson, M. Devenney, D. Giaquinta, J. Golden, R. Haushalter, E. McFarland, D. Poojary, C. Reaves, W. Weinberg and D. Xu, Science, 279 (6), 837, 1998. 6. G. J. Lewis, D. E. Akporiaye, D. S. Bem, C. Bratu, I. M. Dahl, A. Karlsson, R. C. Murray, R. L. Patton, M. Plassen and R. Wendelbo, 13th IZC, July, 2001, in press. 7. R. Broach and G. Lewis, unpublished results, 1992. The structure has been published by Whittingham; Zavalij P. Y., Zhang F., Whittingham M. S.; Acta Crystallog., C53, 1738- 1739, 1997. 8. M. Lafontaine, A. Le Bail and G. Ferey, 3". Solid State Chem., 85, 220-227, 1990. 9. R. Broach and G. Lewis, unpublished results, 1993. The structure was solved from single crystal data. 10. A. Wells, Structural Inorganic Chemistry, FitCh Ed., Oxford University Press, New York, 1986, p. 650. 11. D. Akporiaye, Microporous and Mesoporous Materials, ZMPC 2000, Sendai, Japan, August 2000, in print. 12. D. Bem, J. Sherman, A. Napolitano, A. Leon-Escamilla, G. Lewis and R. Bedard, US Patent 5,888,472, 1997. 13. D. Bem, R. Bedard, R. Broach, A. Leon-Escamilla, J. Guisselquist and J. Pluth, Mater. Res. Soc. Symp. Proc., 1999, 549 (Advanced Catalytic Materials- 1998), 73-78. 14. J. Sherman, D. Bern, G. Lewis, US Patent 6,099,737, 2000.
Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
123
The Local Structures of Transition Metal Oxides Incorporated in Zeolites and their Unique Photocatalytic Properties Masakazu Anpo* and Shinya Higashimoto Dept. of Applied Chemistry, Graduate School of Engineering,Osaka Prefecture University Gakuen-cho, Sakai, Osaka 599-8531, Japan. e-mail: [email protected] Zeolite catalysts incorporated or encapsulated with transition metal cations such as Mo 6§ V 5+, or Ti 4§ into the frameworks or cavities of various microporous and mesoporous molecular sieves were synthesized by a hydrothermal synthesis method. A combination of various spectroscopic techniques and analyses of the photocatalytic reaction products has revealed that these transition metal cations constitute highly dispersed tetrahedrally coordinated oxide species which enable the zeolite catalysts to act as efficient and effective photocatalysts for the various reactions such as the decomposition of NOx into N2 and 02 and the reduction of CO2 with H20 into CH3OH and C H 4 . Investigations on the photochemical reactivities of these oxide species with reactant molecules such as NO• hydrocarbonds, CO2 and H20 showed that the charge transfer excited triplet state of the oxides, i.e., (Mo 5+ -O-)*, (V 4+- O')*, and (Ti 3+ - O-)*, plays a significant role in the photocatalytic reactions. Thus, the present results have clearly demonstrated the unique and high photocatalytic reactivities of various microporous and mesoporous zeolitic materials incorporated with Mo, V, or Ti oxide species as well as the close relationship between the local structures of these transition metal oxide species and their photocatalytic reactivities. 1. INTRODUCTION It is hopefully expected that mankind will strive for the recovery and preservation of a better greener environment with the establishment of environmentally-friendly, clean, safe, and sustainable technologies for the 21 st Century. However, up until now, environmental pollution and destruction on a global scale as well as the lack of sufficient clean energy supplies have drawn much attention and concern to the vital need for ecologically clean chemical technology, materials, and chemical processes, the most important challenge facing chemical scientists today. Although we are moving in a positive direction in the development of such clean and safe chemical systems using photofunctional materials such as titanium oxide photocatalysts, we have yet to gain a complete understanding of the reaction mechanisms for the design of highly efficient and selective photo-induced reaction systems. In recent years, increasing attention has been focused on studies concerning the production of new zeolite materials such as microporous and mesoporous molecular sieves due to their very unique and interesting physicochemical properties such as a pore structure of a molecular scale, the capacity for ion-exchange, a strong surface acidity and a unique
124 with transition metal oxide species, such as M o, V, or Ti-oxides, are of special interest due to their high and unique catalytic and photocatalytic properties [1,2]. Thus, it is very important to obtain detailed information on the effect of the zeolite framework structure on the chemical function of these metal oxide species as well as on the relationship between the local structures of these oxide species and their photocatalytic reactivities. The present study deals with the characterization of the active sites of various hydrothermally synthesized zeolite materials which include the Mo, V, or Ti-oxide species within their frameworks and cavities, and their photocatalytic reactivities including the detection of the intermediate species. Variousmolecular spectroscopic methods such as insitu photoluminescence, ESR, XAFS (XANES and FT-EXAFS), were employed along with analyses of the reaction products to clarify the reaction mechanisms at the molecular level. 2. EXPERIMENTAL The M o-MCM-41 mesoporous molecular sieves (0.5, 1.0, 2.0, 4.0 M o wt%) were synthesized using tetraethylorthosilicate (TEOS) and (NH4)6Mo7024"4H20 as the starting materials and cetyl trimethylammonium bromide (CTMABr) as the template, in accordance with previous literature [3]. Vanadium silicalites (VS-1 and VS-2; 0.2 wt% as V) were prepared by hydrothermal synthesis using tetraethylorthosilicate (TEOS), VOSO4 and VCI3 as the starting materials, and tetrapropylammonium hydroxide (TPAOH), and tetrabutylammonium hydroxide (TBAOH) as a structure directing agent, respectively, under conditions reported in previous literature [4,5]. The V-HMS mesoporous molecular sieve (0.2 wt% as V) was synthesized using tetraethylorthosilicate (TEOS) and VOSO4 and dodecylamine (DDA) as the structure directing agent under conditions reported in previous literature [3]. The V/SiO2 catalyst (0.2 wt% as V) was prepared by an impregnation method of SiO2 with an aqueous solution of NH4VO3. After the products were recovered by filtration, washed with distilled water several times and dried at 373 K for 12 h, calcination of the samples were carried out under a dry flow of air at 773 K for 8 h. TS-1 and TS-2 (Si/Ti -- 85), Ti-MCM-41 (Si/Ti - 100) and Ti-MCM-48 (Sifri -- 80) were hydrothermally synthesized according to procedures previously reported [6,7].-. Ti/FSM-16 and Ti/Vycor glass were prepared by a chemical vapor deposition method (CVD) of the Tioxides onto FSM-16 or Vycor glass, respectively, through a facile reaction of TiCh with the surface OH groups of these supports in the gas phase at 453-473 K, followed by treatment with water vapor to replace the chlorine atoms with the OH groups [8,9]. A TiO2 powdered catalyst, JRC-TIO-4 (anatase 92 %, rutile 8 %), supplied by the Catalysis Society of Japan, was used. Prior to spectroscopic measurements and photocatalytic reactions, the catalysts were degassed at 773 K for 2 h and calcined in 02 (> 20 Torr) at 773 K for 2 h, then degassed at 473 K for 2 h. The photoluminescence and lifetimes were measured at 77 K with a Shimadzu RF-501 spectrofluorophotometer and an apparatus for lifetime measurements, respectively. The ESR spectra were recorded with a JEOL-2X spectrometer (X band) at 77 K. XAFS (XANES and EXAFS) spectra were obtained at the BL-10B facility of the High Energy Acceleration Research Organization (KEK) in Tsukuba. The XAFS spectra of the
125 dehydrated samples were recorded at the M o K-edge, Ti, and V K-edge absorption in the transmittance and fluorescence mode at 293 K, respectively. The EXAFS data were examined by an analysis program by Rigaku EXAFS (REX). The photocatalytic reactions of NO in the absence and presence of the CO molecules were carried out at 298 K with a high pressure mercury lamp through an UV cut filter (/l > 270 nm). The products were analyzed by online gaschromatography. 3. RESULTS AND DISCUSSION
3.1. Molybdenum Oxide Catalysts Results of the XRD patterns and the BET surface area of the Mo-MCM-41 catalysts indicated that they have a hexagonal lattice having mesopores larger than 2 0 A and that they possess a high BET surface area (-- 1000 m2/g) as compared with amorphous silica (300 m2/g), so that they can be considered effective photocatalysts [3]. From analyses of the XAFS (XANES and EXAFS) spectra, it was found that M oM CM-41 in the lower loadings of the M o-oxides (1.0 M o wt%) include highly dispersed tetrahedrally coordinated M o-oxide species, having two shorter M o-O bonds and two longer ones, while the M o-MCM-41 in higher loading amounts of Mo-oxides (4.0 M o wt%), tetrahedrally coordinated M o-oxides (M oO42")n with an additional M o-O-M o bond could be observed [ 10]. M o-M CM-41 (1.0 M o wt%) exhibits a photoluminescence spectrum at around 400-600 nm upon excitation at around 295 nm (defined as X), which coincides with the photoluminescence spectrum of the tetrahedrally coordinated M o-oxides highly dispersed on SiO2, as shown in Fig, 1 [11]. The excitation and emission spectra are attributed to the following charge transfer processes on the M o-O moieties of the tetrahedral molybdate ions (MOO42), involving an electron transfer from the 0 2- to M o 6+ ions and a reverse radiative decay from the charge transfer excited triplet state [2,11 ]. hv
[ M 0 6+-
hv' [ M o s+ - O" ]
O 2" ]
absorption
W [ M 0 6+ photoluminescence
-- 0 2- ]
The width and the wavelength at the maximum intensity of the emission band do not change upon varyingthe excitation wavelength, indicating that there is only one emitting site with a photoluminescence lifetime of 2.25 ms at 77 K. These results indicate that the M ooxides showing absorption in the region of 295 nm form a tetrahedral coordination in a highly dispersed state. On the other hand, as shown in Fig, 2, there are at least two luminescent species (the absorption spectrum can be deconvoluted into two components having wavelength regions of X and Y in Fig. 3 at 295 and 310 ran, respectively) on Mo-MCM-41 (4.0 Mo wt%) [12]. The increase in M o content, from 1.0 to 4.0 M o wt%, leads to the formation of not only the emitted X site with a photoluminescence lifetime of 2.25 ms but also another emitting site (in the region of Y) probably induced by M o-M o interactions via the oxygen ions (M o-O-M o), which cause a more efficient radiationless energy leading to a decrease in the
126 photoluminescence lifetime (0.91 ms). Taking into account the XAFS data, only the isolated tetrahedrally coordinated M o-oxides are formed in lower M o loadings, while two types of tetrahedrally coordinated M o-oxides at highly dispersed levels and (M 0042-) n are formed in higher Mo loadings, as shown in Fig. 3.
A a't
(a) )
(A)
5
(el
.z,
(e)
J 9b(Y)
(/) E:
.
(b)
._c m
(x
.>
~ff.
)
Ar I, 200
.~~
300
400
500
Wavelength / nm
Fig. 1. Effect of the addition of NO on the photoluminescence spectrum and the excitation spectrum of Mo-MCM-41 with loading amount of 1.0 Mo wt%. Pressure of added NO : (A, a) 0; (b) 0.07; (C, c) 0.4 Torr; (d) excess; (e) degassed after (d).
(a)
Sl
H
\Z ";" \o
2,1,.,. 300
400
600
Fig. 2. Effect of the addition of NO on the photoluminescence spectrum and the excitation spectrum of Mo-MCM-41 with a Si/Mo ratio of 40. Pressure of added NO : (A, a) 0; (b) 0.6; (C, c) 4 Torr; (d) excess; (e) degassed after (d). Spectrum (A) can be deconvoluted into (X) and (Y).
O
.O
Q
1.74A~kk / 3.1~9A~ // /
500
Wavelength / nm
(b)
,.r~A
~, .//Mo
200
600
(c)
(c)
o
/H
d9o/
Fig. 3. Proposed local structures of the isolated (a) as well as oligomeric Mo-oxide sites (b) in the Mo-MCM-41 catalyst.
3.1.1. Photocatalytic Decomposition Reaction of NO by the Coexistence of Additive Gasses on the Mo-MCM-41 Catalysts and their Photocatalytic Reactivity The photocatalytic decomposition reactions of NO in the absence and presence of various kind of additive gases such as CO, propane, ethane, methane, and propylene were performed on M o-MCM-41 under UV-irradiation (X > 270 nm). No products could be detected under dark conditions nor did the silicious M CM-41 or bulk M 003 exhibit any photocatalytic reactivities. However, UV-irradiation of Mo-MCM-41 in the presence of NO led to the evolution of N2 as well as N20 and NO2. It was found that the efficiency of
127 the photocatalytic decomposition reactions of NO strongly depended on the kind of additives used. The order of the reactivity for the photocatalytic decomposition reactions is as follows: CO > propane > ethane > propylene -- methane. In line with these results, further investigations showed that the photocatalytic decomposition reactions of NO exhibited high efficiency by the coexistence of propane and CO. The photocatalytic decomposition of NO into N2 and CO2 on M o-M CM-41 was found to proceed effectively and efficiently by the coexistence of CO. As shown in Fig, 4, UVirradiation (A > 270 nm) of M oMCM-41 in the presence of a
Fig, 4. Reaction time profiles of the decomposition reaction of NO by the CO on M o-M CM-41 (1.0 M o wt%). (A), N2 (11), N20 ( O ) ; conversion
photocatalytic coexistence of Yields of CO2 of NO (C)).
Amount of added NO or CO: 180 /z mol-g-catl
mixture of NO and CO led to the formation of N2 and CO2 with a good linearity against the UV-irradiation time as well as a good stoichiometry, while the turnover frequency exceeded unity after irradiation for 2h. These results clearly indicate that the reaction proceeds photocatalytically. Also, atter UV-irradiation for 3 h, NO conversion and selectivity for the formation of N2 reached close to 100 %, leading to the formation of small amounts of N20 during this reaction in the gas phase [ 13,14]. UV-irradiation of Mo-MCM-41 in the presence of CO alone and its subsequent evacuation at 293 K led to an efficient quenching of the photoluminescence, which suggests ..
that the charge transfer excited triplet state of the [M 05+ - O-]* complex reacts with CO, leading to the formation of M o4+ ions as well as CO2, which exhibits no ESR signals due to the M 05+ ions [ 13-16]. Exposure of the NO molecules into the photo-formed M o4+ ions led to the formation of N20 under dark conditions. In fact, after subsequent evacuation, the photoluminescence intensity recovered, but not to its original photoluminescence intensity due to the formation of carbonyl species such as [M 04+ - CO] which decompose only upon heating at temperatures above 373 K [ 17]. In fact, the exposure of NO and N20 onto M o4+ ions under dark conditions led to the formation of N20 and N2, respectively. From these results, the photocatalytic decomposition reaction mechanism of NO by the coexistence of the CO reaction can be proposed, as shown in Scheme 1. After the subsequent evacuation of the catalyst, the photoluminescence intensity recovered accompanied by the oxidation of Mo 4+ to Mo 6+ ions. In-situ photoluminescence and ESR measurements demonstrated that this reaction proceeds in a redox cycle between alternating M 06+ and M o4+ ions, i.e., it was
128 found that the photo-formed M o4+ ions, through a reaction of the charge transfer excited triplet state with CO, are oxidized to the original M 06+ ions in the presence of NO or N20, leading to the formation of N2. (MOs+- O')*
hl ~I/ h V
cited triplet state of t h e ~ S xtetrahedral!y coordinated Mtor_oxides )
(M06+= OZ-) ff etrahedrallycoordinated Mo-oxides)
~~----
N2 [ t - - ' t
ated
CO
~,., L,u ~ C O 2
(M04+)
CO2
(M~4+) NO
~ ~ . .
(M06+," ~ ' x
NO
Scheme 1. Catalytic cycles for the photocatalytic decomposition of NO in the coexistence of CO.
3.1.2. Relationship between the Local Structures of Mo-oxides and their Photocatalytic Reactivities for the Decomposition of NO by the Coexistence of CO Photoluminescence and XAFS investigations of M oMCM-41 were performed and the results revealed that the absorption in the X and Y regions are attributed to tetrahedrally coordinated Mooxides at a highly dispersed level and (M 0042-) n, respectively. Figure 5 shows the parallel relationship between the yields of N2 formation for the decomposition of NO on MoMCM-41 (0.5-4.0 M o wt%) by the coexistence of CO and the relative intensity of the absorption spectra observed in the total region (X and Y) of the catalyst. The intensities of the
Fig, 5. Relationships between the yields of N2 formation for the photocatalytic decomposition reactions of NO by the coexistence of CO, and the relative intensity of the absorption in the total region of (X and Y) of M o-M CM-41 (0.5, 1.0, 2.0, and 4.0 M o wt%). Added NO or CO: 180 tt mol-e-cat. -I
129 absorption spectra of two types of tetrahedral M o-oxides in the total region of X and Y were found to have a good relationship with the yields of N2 for the photocatalytic decomposition of NO in the presence of CO [13]. These results indicate that in the presence of CO, two types of tetrahedral M o-oxides at a highly dispersed level as well as (M 0042) n work as the active sites. 3.2. Titanium Oxide Catalysts
The development of efficient photocatalytic systems which are able to decompose NO directly into N2 and O2 or to reduce CO2 with H20 into chemically valuable compounds such as CH3OH or CH4 are among the most described yet and challenging goals in the research of enviromentally-friendly catalysts. From this point of View, much attention has been focused on the useful application ofTi-oxide photocatalysts, mainly as TiO2 semiconductors, TiO2 thin films, and isolated tetrahedrally coordinated Ti-oxides [1,2]. Recently, we have reported that highly dispersed tetrahedrally coordinated Ti-oxides, when compared with bulk TiO2 powder, exhibit high and unique photocatalytic reactivity for the NO decomposition reaction as well as the reduction of CO2 with H20 [1,8,9]. It can be seen that understanding the relationship between the local structure of the Ti-oxides and their photocatalytic reactivity, especially their selectivity among various types of Ti-oxide catalysts is of special importance. In-situ characterizations of Ti-oxides included within various types of zeolites or anchored on support surfaces by means of UV-Vis, ESR, photoluminescence and XAFS (XANES and EXAFS) investigations provided important insights into their local structure and their photocatalytic reactivity for the decomposition of NO into N2 and 02 as well 100 , ~ as the reduction of CO2 with H20 into .~ Ileal,." CH3OH and CH4. It was found that Ti- c 8 0 " o12~ o oxides prepared within zeolites or on ~ oasupport surfaces exhibit quite different and ~ 60 o.~"rl ~ o 2 high photocatalytic reactivity as compared o oa-" ~ /Oa" 0 2to bulk powdered TiO2 and also that the high z 6 - ~ [i reactivity of the charge transfer excited o 4 0 " II 02triplet state of the tetrahedrally coordinated ~iTi-oxides, (Ti 3+ - O-)*, plays a significant _~ 20 role in the unique and high photocatalytic 0~ reactivity of these catalysts. I t I I XAFS (XANES and EXAFS) 03.5 4 4.5 5 5.5 6 6.5 investigations of these Ti-oxide catalysts at Coordination Number the T i K-edge were carried out and the results revealed the Ti-oxides to have a Fig, 6. Relationship between the coordination number of the Ti-oxides and the tetrahedral coordination within the Ti-oxide catalysts, while the Ti-oxides have an selectivity for N2 formation in the octahedral coordination in the case of the photocatalytic decomposition of NO into N2 and 02 on various titanium oxide catalysts. bulk TiO2 photocatalyst. Figure 6 shows
130 the relationship between the coordination number of the Ti-oxides and the selectivity for N 2 formation in the photocatalytic decomposition reaction of NO on various Ti-oxide photocatalysts. The clear dependence of the N2 selectivity on the coordination number of the Ti-oxides can be observed, i. e., the lower the coordination number of Ti-oxides, the higher the N2 selectivity [1]. From these results, it can be proposed that a highly efficient and selective photocatalytic decomposition of NO into N2 and 02 can be achieved using Ticontaining zeolites as a photocatalyst which involves highly dispersed tetrahedrally coordinated T i-oxides as the active species. The reactivity of such a charge transfer excited state was also found to strongly depend on the differences in the molecular environment of the T i-oxides such as the rigidity or flexibility of the zeolite framework and the local structures of the TiO 4 unit, i. e., Ti(OSi)4, Ti(OH)(OSi)3 or Ti(OH)2(OSi)2 [ 1,18,19]. 3.3. Vanadium Zeolite Catalysts Zeolites having V-oxides in their frameworks have been the focus of much attention for their interesting and distinctive physico-chemical properties as well as photocatalytic reactivities. So far, several types of vanadium silicalite catalysts in which vanadium ions are incorporated into the zeolite framework have been developed, however, the true chemical nature and reactivities of these vanadium silicalites are yet little known.. The results of XAFS (XANES and EXAFS), ESR, photoluminescence and FT-IR measurements of such Vsilicalites (VS-1 and VS-2), V-HMS, and V/SiO2 have shown that they include highly
dispersed tetrahedrally coordinated V-oxides having one oxygen in the shorter V-O distance and three oxygen atoms in the longer V-O distance within the zeolitic framework or on the silica surface. These V-oxide catalysts exhibited a phosphorescence spectrum attributed to the radiative decay from the charge transfer excited triplet state [ 1,2,20]. Table 1 shows a comparison of the chemical properties of the VO4 unit of the various types of V-oxide catalysts. The values of the vibrational transition energy between the (0 ---~ Table 1. Comparison of the various physical and chemical parameters of the Voxide species formed within the zeolite frameworks and SiO 2 surface. Photocatalysts
VS-I
VS-2
WSiO 2
V-HMS ,
Coordination
tetrahedral
tetrahedral
1.68
1.66
1.63
1.62
V-O bond length, (A)
1.78
1.77
1.77
1.78
V=O vibrational energy, (cm-1)
960
980
1010
1035
Lifetime of the excited state, (ms)
5.8
6.9
7.6
V=O bond length, (A)
tetrahedral
tetrahedral
,.
O=V-O bond angle, ( 4~)
4~1
___
4~2
<
4~3
8.4 <__
4~4
131 0) and (0 ~ 1) transition bands calculated from the second-derivative phosphorescence spectra of VS-1, VS-2, V-HMS, V/SiO2 were found to be about 960, 980, 1010 and 1035 cm -~, respectively, and they are attributed to the vibrational transition having a V=O vanadyl bond, showing that they correspond with the decrease in the V=O bond distance from 1.68/~ to 1.62 ~. Moreover, the phosphorescence lifetimes ofVS-1, VS-2, V-HMS and V/SiO2 were found to be about 5.8, 6.9, 7.6 and 8.4 ms at 77 K, respectively. The increase in the lifetime from 5.8 to 8.4 ms can be interpreted in terms of an increase in the distortion of the VO4 unitand a decrease in the V=O bond length [20,21 ]. These results indicate that the VO4 unit incorporated within the V-silicalites has a Td-like 0 asymmetrical structure and exhibits a smaller O:V-O-(Si, H) bond angle than that of V-HM S or V/SiO2 on the basis of the VSEPR (valence shell electron pair repulsion) theory, as / O t:=="~~ O shown in Fig. 7 [21]. It is well known that V-silicalites have a rigid zeolite framework structure while V-HM S has si \ O Si a greatly flexible structure. Taking these results into consideration, the zeolitic rigid framework structure of Vsilicalites causes a more significant and pronounced effect Si on the chemical properties of the VO4 unit than the flexible Fig. 7. Structure of Vframework structure ofV-HMS, which is similar to V/SiO2. oxide species. Furthermore, the dynamic quenching of the phosphorescence by adding reactant molecules showed that the charge transfer excited trip let state of these tetrahedrally coordinated V-oxides plays a significant role in the photocatalytic decomposition reaction of NO.
%*
I
4. C O N C L U S I O N S Unique and efficient photocatalytic systems incorporating transition metal oxides (M o, Ti, V) have been designed using the cavities and frameworks of zeolites and mesoporous molecular sieves. The present results have demonstrated the unique ph~csicochemical properties of the local structure of such anchored metal oxides, which were theresult of the rigidity or flexibility of the zeolite framework, as well as their photocatalytic reactivities. These well-defined photocatalysts can be considered one of the most promising candidates for use in the environmentally-friendly reaction systems. REFERENCES
1. 2. 3. 4. 5. 6.
M. Anpo (eds.), in Photofunctional Zeolites, NOVA Publishers Inc. (2000). M. Anpo and M. Che, Adv. Catal., 44 (1999) 119, and references therein. W. Zhang, J. Wang, P. T. Tanev, and T. J. Pinnavaia, J. Chem. Soc., Chem. Commun., (1996) 979. H.P. Rao, P. R. Ramaswamy, V. P. Ratnasamy, J. Catal., 137 (1992) 225. M.S. Rigutto, H. Van Bekkum, Appl. Catal., 68 (1991) 297. S.G. Zhang, Y. Ichihashi, H. Yamashita, T. Tatsumi, and M. Anpo, Chem. Lett., (1996) 895.
132 7.
S.G. Zhang, Y. Fujii, H. Yamashita, K. Koyano, T. Tatsumi, and M. Anpo, Chem. Lett., (1997) 659.
8.
M. Anpo, N. Aikawa, Y. Kubokawa, M. Che, C. Louis and E. Giamello, J. Phys. Chem., 89 (1985) 5017.
9.
K. Ikeue, H. Yamashita, M. Anpo, Chem. Lett., (1999) 1135.
10. S. Higashimoto, R. Tsumura, M. Matsuoka, H. Yamashita, M. Che, M. Anpo, submitted to Stud. Surf. Sci. Catal. 11. M. Anpo, M. Kondo, S. Coluccia, C. Louis, and M. Che, J. Am. Chem. Soc., 111 (1989) 8791. 12. S. Higashimoto, R. Tsumura, S. G. Zhang, M. Matsuoka, H. Yamashita, C. Louis, M. Che, and M. Anpo, Chem. Lett., (2000) 408. 13. R. Tsumura, S. Higashimoto, M. Matsuoka, H. Yamashita, M. Che, M. Anpo, Catal. Lett., 68 (2000) 101. 14. R. Subbotina, B. N. Shelimov, V. B. Kazansky, A. A. Lisachenko, M. Che, and S. Coluccia, J. Catal., 184 (1999) 390. 15. B.N. Shelimov, A. N. Pershin, and V. B. Kazansky, J. Catal., 64 (1980) 426. 16. N. Pershin, B. N. Shelimov, and V. B. Kazansky, Kinet. Katal., 21 (1980) 494. 17. C. Williams and J. G. Ekerdt, J. Phys. Chem., 97 (1993) 6843. 18. L. Marchese, T. Maschmeyer, E. Gianotti, S. Coluccia, and J. M. Thomas, J. Phys. Chem. B, 101 (1997) 8836. 19. M. Anpo, S. Higashimoto, Y. Shioya, K. Ikeue, M. Harada, M. Watanabe, submitted to Stud. Surf. Sci. Catal. 20. M. Anpo, S. Higashimot6, M. M atsuoka, H. Yamashita, Y. Shioya, S. Dzwigaj, and M. Che, submitted to ,/. Phys. Chem. 21. S. Dzwigaj, M. Matsuoka, R. Franck, M. Anpo, and M. Che, J. Phys. Chem. B 102 (1998) 6309.
Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
SUMMARIES
133
of O R A L P R E S E N T A T I O N S
12 - In-Situ Spectroscopy and Catalysis (Mondayam) 12-O-01 - 2D correlation IR spectroscopy of xylene isomerisation on H-MFI zeolite F. Thibault-Starzyk*, A. Vimont and J.-P. Gilson Laboratoire Catalyse & Spectrochimie, CNRS ISMRA, Caen, [email protected], France New data treatment methods such as 2D correlation infrared spectroscopy (2D-COS) lead to significant improvements for in situ studies. We report here the application of 2D-COS to the in situ infrared study of orthoxylene isomerisation in H-MFI zeolite in working conditions. This led to improve the quantitative monitoring of xylene isomers in the micropores of the solid and to the detection of ffaces of coke in the catalyst. A correlation was found between coke and the perturbation of specific hydroxy groups in the solid.
12-O-02 - Structure/reactivity correlation in Fe/ZSM5 applications. In-situ XAFS characterization and catalysis
for
deNOx
A.A. Battiston, J.H. Bitter, D.C. Koningsberger Department of Inorganic Chemistry and Catalysis, Utrecht University, The Netherlands
In-situ XAFS spectroscopy performed at 350 ~ shows that in Fe/ZSM5 synthesized through the FeCI3 sublimation technique (Si/AI - !7) Fe is predominantly present in the form of binuclear oxo/hydroxo-complexes. During reaction with i-C4Hl0 a clear reduction in the oxidation state of the iron is detected, accompanied by changes in only one of the three Fe-O shells. This confirms the presence of a specially reactive oxygen and demonstrates the possibility of XAFS of studying the local environment around iron in Fe/ZSM5 under experimentally realistic conditions (in-situ, at 350~
12-O-03 - Interaction of diazines with faujasites studied by IR spectroscopy, temperature-programmed desorption, and molecular modeling methods J. D6bler (a), E. Geidel (a), B. Hunger (b), K.H.L. Nulens (c) and R.A. Schoonheydt (c) a Institut fiir Physikalische Chemie, Universitgit Hamburg, [email protected], Germany, b Wilhelm-Ostwald-Institut, Universitgit Leipzig, Germany, c Centrum voor Oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Belgium The adsorption behavior of diazines in X and Y zeolites has been studied by infrared spectroscopy (IR), temperature-programmed desorption (TPD), and simulation techniques. The studies showed that the interaction is determined by a donation of electron density from the nitrogen atoms of the probe molecules to the Lewis-acidic cations. The individual nature of the adsorption strongly depends on the Si/A1 ratio of the zeolites, the kind of extraframework cation, and the positions of heteroatoms in the probe molecules.
134 1 2 - O - 0 4 - D R I F T study of dinitrogen and dihydrogen adsorption on Li- and Na- forms of LSX zeolite V.B. Kazansky(a), A.I. Serykh(a), E. Tichomirova(a), V.Yu. Borovkov(a) and M. Bulow(b)
a Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia, [email protected], b BOC GASES, Technical Center, Murray Hill NJ, USA Adsorption of H2 at 77 K on Li-LSX zeolite with DRIFT control of perturbation of adsorbed molecules has discriminated three different types of adsorption sites. Two of them were ascribed to H2 adsorption on Li + ions localized in supercages of the zeolite framework at Sm and SIII' sites, while the latter one most likely belongs to H2 adsorption on Li + ions at SII sites. Adsorption of N2 by Li + ions at SIII and SIII' sites is the strongest resulting in a decrease of intensity of the corresponding DRIFT bands from adsorbed H2. N2 dsorption by Li + at Su sites is very much weaker. 0 6 - Fundamentals of Miceile Templating (Monday am) 06-O-01
- The effect of stoichiometry and synthesis conditions on the
properties of mesoporous M41S family silicates W.J. Roth and J.C. Vartuli
ExxonMobil Research and Engineering, Annandale, USA wieslaw_j [email protected], james c [email protected] Basic quantitative relationships and trends governing the formation of the M41S mesoporous molecular sieves MCM-41 and MCM-48 are presented. The syntheses with hydroxide/surfactant molar ratio close to unity afforded high quality MCM-41 and proved particularly suitable for quantifying the effects of synthesis mixture composition and synthesis conditions upon the nature and properties of the mesoporous products. Increasing temperature and duration of crystallization resulted in unit cell expansion and a more robust silica framework. Syntheses with silica to surfactant molar ratio equal to 5:1 and higher gave MCM-41 while MCM-48 was observed at lower (3.5:1) ratios. 0 6 - 0 - 0 2 - What are circular crystals? F. Marlow
MPI fiir Kohlenforschung, 45470 Miilheim/Ruhr, [email protected], Germany Translational symmetry is usually considered a pre-requisite for a perfect long range organization of matter. This is realized for crystals in all three dimensions. However, we have found materials architecture with perfect long range three dimensional order and no translational symmetry. The first example are mesostructured silica fibers consisting of channels wound around the fiber axis, thereby forming an array with hexagonal short range order. The whole structure is controlled by a singularity which is the fiber axis. In reciprocal space, the fibers are represented by a system of rings instead of a reciprocal lattice known for crystals. A physical consequence of this are unusual X-ray diffraction properties. Because of the new reciprocal space representation the circular architecture has to be regarded as a qualitatively new form of solid state organization.
135
0 6 - 0 - 0 3 - Hierarchically mesostructured zeolitic materials with the MFI structure D. Trong On a, P. Reinert b, L. Bonneviot b and S. Kaliaguine a
aDepartment of Chemical Engineering, Laval University, Ste Foy, Quebec, Canada blnstitut de Recherche sur la Catalyse, CNRS UPR-5401, Villeurbanne, France A new approach for the synthesis of mesostructured zeolitic materials (namely UL-TS-1 and UL-ZSM-5) is reported. The materials were obtained in the solid state by heating TPAOHimpregnated mesoporous materials for several days. Various techniques including XRD, N2 adsorption, UV-visible, FTIR, TEM and 29Si MAS NMR were used to monitor the physicochemical properties of these materials as a function of crystallization time. The increase in the percentage of crystallinity is correlated with the corresponding variations in micropore and mesopore volumes, BET and BJH surface areas. The results indicate that the mesopore walls consist of zeolite nanocrystals. Depending on crystallization time, a range of materials from totally amorphous up to 80% crystalline is observed, while some of mesopores are preserved.
0 6 - 0 - 0 4 - Pore size engineering of M C M - 4 8 : the use of different additives as expanders M. Mathieu, E. Van Bavel, P. Van Der Voort and E.F. Vansant
Dept. of Chemistry- Laboratory of Adsorption and Catalysis, University of Antwerp (U.LA.), Wilrijk, Belgium, [email protected] For the first time the pore size engineering of mesoporous MCM-48 materials using several additives during the synthesis is discussed. It was shown that dimethyltetradecyl amine (DMTDA) is a convenient expander, resulting in a MCM-48 structure with a pore size enlargement from 1.7 nm to 2.4 nm pore radius. Also a wide range of dimethylalkyl amines, with varying chain length were applied as swelling agents. Hereby, the influence of the chain length and the effect of the molar ratio of amine/surfactant on the crystallinity and pore size of the MCM-48 were studied. Other additives, such as ethanol and decane, were also found to be suitable for the synthesis of large pore MCM-48. 10 - Host-Guest Chemistry (Monday am)
10-O-01 - Investigation of indium loaded zeolites and additionally promoted catalysts for selective catalytic reduction of NOx by methane F.-W. Schtitze W. Grtinert b
a, H. Berndt a, M. Richter a, B. Lticke a, C.
Schmidt b, T. Sowade b and
Institut[ar Angewandte Chemie Berlin-Adlershof (ACA), Berlin, Germany," [email protected] Lehrstuhl fur Technische Chemie, Ruhr-Universitdt-Bochum, Bochum, Germany The nature of active sites of In zeolites and their function and behavior in the SCR of NO• with methane has been investigated. In zeolite structures (mordenite, ZSM-5) were prepared by various methods. The catalysts were additionally promoted by oxidic components, above all CeOx, to improve their activity as well as to stabilize their performance in the presence of water vapor. The obtained composite materials showed promising activity under reaction conditions. The promoting effect of the oxidic components will be discussed shortly.
136
10-O-02 - Ion exchange of alkali metals and control of acidic/basic properties of MCM-22 and MCM-36 J.-O. Barth, R. Schenkel, J. Kornatowski and J.A. Lercher
Technische Universitdt Mfmchen, Lehrstuhl Il fi~r Technische Chemie, Munich, Germany jan-olaf barth@ch, tum. de MCM-22 (Si/AI = 12) and MCM-36 pillared with SiO2 (Si/AI = 29) were modified by ion exchange of alkali cations. A critical point was the pH of the solution, which should be adjusted to about 9 and 4, respectively. At pH 9 the pillared mesoporous structure of MCM36 was destroyed as indicated by nearly amorphous XRD patterns and severely reduced BET surface areas. The degree of exchange decreased from Na to Cs (except the lowest value for Li). In spite of this, the basic character in both series increased from Li to Cs as demonstrated by IR spectra of adsorbed pyridine and TPD of ammonia.
10-O-03 - Insertion compounds of metal halides with porosils: "Structured Gases" P. Behrens (a), M. Hartl (a), G. Wirnsberger (b), A. Popitsch (b) and B. Pillep (c)
a) Institut fiir Anorganische Chemie, Universitat Hannover, Hannover, Germany," Peter.Behrens@ mbox.acb.uni-hannover.de; b) Institut ffir Physikalische und Theoretische Chemie, Technische Universitdt Graz, Austria; c) Patent- und Rechtsanwaltskanzlei Kador & Partner, Mfinchen, Germany Insertion compounds of porosils with mercury(II) halides HgX2 (X: C1, Br, I) and with gold(Ill) chloride were synthesized and characterized by a variety of analytical techniques. Due to the electroneutral character of the pure SiO2 framework of the porosil hosts, host-guest interactions are restricted to weak forces of the van der Waals-type. The compounds contain isolated HgX2 molecules or Au2C16 dimer molecules, respectively. These molecules have properties that are very similar to the corresponding molecules in the gaseous state.
10-O-04 - Site selective adsorption and catalytic properties of iron in FER and BEA zeolites Z. Sobalik, J.E. ~;poner, Z. Tvarfl~kov/t, A. Vondrov~i, S. Kuriyavar and B. Wichterlovfi
J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic- Sobalik@l'h-inst.cas.cz FTIR spectroscopy, interaction with oxygen, NO, N20, catalytic oxidation of NO to NO2, and reduction of NOx with propane have been used to characterise Fe cations in FER and BEA zeolites. Three cationic positions for Fe ions in dehydrated samples of Fe-FER, and one in FeBEA have been identified. A complex nature of the reversible interaction of the Fe(II) cations in FER and BEA with 02, NO, N20 has been described. The experimental study is complemented with a simple theorical investigation of Fe(II) and Fe(III) coordination over the most populated 13 site.
137
17 - Principles of Adsorption (Monday am) 17-O-01 - Liquid-solid and solid-solid phase transitions of oxygen in a single cylindrical pore K. Morishige and Y. Ogisu Department o f Chemistry, Okayama University of Science, Okayama, morishi@chem, ous. ac.jp, Japan To study the liquid-solid and solid-solid phase transitions of a confined 02, we performed Xray diffraction measurements of O2 confined inside the cylindrical pores of six kinds of regular mesoporous adsorbents (MCM-41 and SBA-15) with different pore radii as a function of temperature. Hysteresis effects between the y-to-J3 and [3-to-)' solid-solid phase transitions are considerably larger than those between freezing and melting and the depression of the [3to-), transition point is slightly smaller than that of the melting point.
17-O-02 - Structural study of benzene, tetrachloroethene and trichloroethene sorbed phases in silicalite-1 N. Floquet a, J.P. Coulomb a, G. Weber b, O. Bertrand b and J.P. Bellat b aC.R.M. C 2 - CNRS, Campus de Luminy, Case 901, 13288 Marseille Cedex 9- France bL.R.R.S. - CNRS, Universit6 de Bourgogne, B.P. 400, 21011 Do'on Cedex - France From our detailed neutron diffraction investigation of the structural properties of C2HCI3, C2C14 and C6D6 sorbed phases in Silicalite-I, we deduce that the steps observed in their adsorption isotherms are not signatures of phase transitions but are correlated to the different stages observed during the Silicalite-I loading. For C6D6 such a loading is a three stages process (the C6D6 molecules fill successively, the intersections, the straight and the sinusoidal channels). Concerning C2C14, it is a two stage process (the C2C14 molecules fill the intersections and after indifferently the straight channels and the sinusoidal channels). Usual sorption is observed for C2HC13 which fills all parts of the Silicalite-I porosity indifferently.
17-O-03 - Molecular ordering of the adsorbed phase within the microporous model aluminophosphate AIPO4-11 at cryogenic temperatures N. Dufau*, N. Floquet**, J-P. Coulomb**, P.L. Llewellyn* and J. Rouquerol* * Groupe MADIREL, C.T.M. du C.N.R.S., 26 rue du 141 ~meR.I.A. 13003 Marseille (France) ** C.R.M. C2., Campus de Luminy, Case 901, 13288 Marseille cedex 9 (France) The present paper highlights the influence of molecular sized micropores on the ordering of the adsorbed phase within AIPO4-11. A range of simple probe molecules was used including: Ar, Kr, CH4, O2, N2 and CO. Their adsorption properties were studied by adsorption microcalorimetry at 77 K and 87 K as well as by neutron scattering measurements in the temperature range from 20 to 100 K.
138 1 7 - O - 0 4 - Adsorption properties o f a supercritical fluid on mesoporous molecular sieves under high pressure Ya. Goto a, N. Setoyama b, Y. Fukushima b, T. Okubo c, Yu. Goto c, Y. Imada c, Y. Kubota c and Y. Sugi c
a) Japan Chemical Innovation Institute, el [email protected], Japan, b) Toyota Central R&D Labs. Inc., 41-1 Yokomichi,Nagakute, Aichi, Japan; c) Faculty of Engineering, Gifu University, Gifu, Japan High pressure argon adsorption isotherms were measured up to 10 MPa on mesoporous molecular sieves with various pore sizes at 303 K. The adsorption properties of argon onto mesopores were energetically analyzed by Langmuir theory. The calculated adsorption energy decreased monotonically with increase of pore diameter even in mesopore range, caused by an enhancement of molecule-surface interaction due to the curvature of pore wall.
2 3 - M i c r o - and Mesoporous Materials in Fine Chemistry (Mondaypm) - Delaminated zeolites as active catalysts for processing large
23-K-01
molecules A. Corma* and V. Forn6s Instituto de Tecnologia Quimica, UP V-CSIC, Universidad Polit~cnica de Valencia, Valencia, Spain - acorma@itq, upv. es Zeolite nanolayers have been obtained by delaminating the lamellar precursors of four zeolites. These materials present very high well structured external surface areas larger than 600 m2.g~. Catalytic active sites can be introduced during the synthesis or by post-synthesis treatments, yielding active and selective catalysts for processing large size molecules of interest in oil refining and for the production of fine chemicals.
23-0-02
- Pd-zeolites as catalysts for the Heck reaction: a screening o f
reaction parameters affecting catalyst heterogeneity M. Dams, D.E. De Vos, L. Drijkoningen and P.A. Jacobs*
Centre for Surface Chemistry and pierre.jacobs@agr, kuleuven, ac. be
Catalysis,
K.U.Leuven,
Heverlee,
Belgium
-
Heck reactions were performed with 4-bromoacetophenone and n-butyl acrylate, yielding the trans-substituted acrylate ester with high selectivity. Pd-mordenite was used as catalyst. The heterogeneous nature of the catalysis largely depends on the solvent used and on the base. With tributylamine as the base and in toluene, the Pd(0)-mordenite catalyzed Heck olefination is truly heterogeneous. The heterogeneous catalyst is less air-sensitive than typical homogeneous palladium catalysts that contain phosphine ligands.
139
2 3 - 0 - 0 3 - B e c k m a n n rearrangement of cyclohexanone oxime over mesoporous M C M - 4 1 - and M C M - 4 8 - t y p e materials R. GRiser, H. Kath and J. Weitkamp*
Institute of Chemical Technology, University of Stuttgart, Stuttgart, Germanyjens. weitkamp@po, uni-stuttgart.de The Beckmann rearrangement of cyclohexanone oxime in the gas phase has been investigated over siliceous MCM-41- and MCM-48-type materials. At 275~ complete conversion occurs for several hours with selectivities for ~-caprolactam up to 65 %, until the catalysts deactivate rapidly. The deactivation of the mesoporous catalysts is considerably reduced as compared to that obtained over an amorphous silica gel. MCM-48 exhibits the highest catalyst lifetime which, for MCM-41-type materials, is longer with larger pore diameter. With an aluminumcontaining H-MCM-41 catalyst an increased ~-caprolactam selectivity is achieved.
23-0-04K n o e v e n a g e l condensation between ethylcyanoacetate and benzaldehyde over base catalysts immobilized on m e s o p o r o u s materials Youngyun Choi, Keun-Sik Kim, Jong-Ho Kim and Gon Seo
Department of Chemical Technology and The Research Institute for Catalysis, Chonnam National University, Gwangju, Korea Three different organic bases, imidazole (IM), triazole (TZ) and hydrogenated 1,8-diazabicyclo(5.4.0) undecene-7 (DBU) were immobilized on mesoporous materials. Immobilized state of organic bases and their catalytic activities in Knoevenagel condensation between ethylcyanoacetate and benzaldehyde was studied. Organic bases immobilized mainly on mesopore still retained their catalytic activities with an inevitable loss due to immobilization. Imidazole catalyst immobilized on KIT-1 disordered mesoporous material with threedimensional channels showed a sufficient activity for multi-repeated use.
2 3 - 0 - 0 5 - One-step synthesis of M I B K from acetone over Pt/X catalysts L.V. Mattos (a), F.B. Noronha (b) and J.L.F. Monteiro (a)
a NUCAT/PEQ/COPPE/UFRJ, [email protected], Brazil," b Instituto Nacional de Tecnologia (INT), bellot@int, gov. br, Brazil The synthesis of MIBK was studied over Pt supported on NaX and CsX zeolites. The activity increased as both the temperature and the Hz/Ac ratio were increased. Temperature had also a beneficial effect on the selectivity to MIBK but the H2/Ac ratio had an opposite effect. Activities and selectivities were always higher for Pt/NaX than for Pt/CsX. For Pt/NaX, increasing the reduction temperature increased the activity but decreased the selectivity to MIBK. Both catalysts were quite stable and selectivities to MIBK of 70 % were obtained over P t ~ a X at 613 K and Hz/Ac = 0.5. The absence of both strong acidic and strong basic sites and a proper balance between metallic and basic sites are responsible for behavior observed.
140
0 2 - Zeolite Nucleation and Growth (Monday pm) 02-O-01 - Small angle X-ray scattering on TPA-Silicalite-I precursors in clear solutions: influence of silica source and cations C.J.Y. Houssin a, B.L. Mojet a, C.E.A. Kirschhock b, V. Buschmann c, P.A. Jacobs b, J.A. Martens b and R.A. van Santen a
a Schuit Institute of Catalysis, Eindhoven, The Netherlands - c.][email protected]; b K. U. Leuven, Leuven, Belgium; c Darmstadt University of Technology, Darmstadt, Germany The formation and growth of crystal nuclei of TPA-Silicalite-1 (aluminium free ZSM-5) from clear solutions using TEOS and silicic acid as silica sources were studied with small angle Xray scattering (SAXS). Information was obtained on the size and shape of nanoscopic precursor particles of silicalite-1. The SAXS data can be interpreted assuming the presence of tablets of 4•215 nm up to 8•215 nm depending on the synthesis conditions. Starting solutions have been studied varying the silica source and the cations content (sodium, potassium and TPA). Although the nanoparticles differ in size, their shape is very similar and these data strenghten our confidence that TPA-Silicalite-1 formation is rather nanoblocks based aggregation mechanism than growth via monomer addition.
0 2 - 0 - 0 2 - Nucleation processes in zeolite synthesis revealed through the use of different temperature-time profiles C.S. Cundy, J.O. Forrest and R.J. Plaisted
Centre for Microporous Materials, UMIST, colin,[email protected], uk, UK A comparison between thermal and microwave syntheses of colloidal silicalite-1 has provided a clear demonstration of the separate contributions of room-temperature ageing, heating rate and synthesis temperature to the nucleation process. At ageing times up to about 50 days, the product crystal size obtainable from a single synthesis composition is sensitive to reaction temperature and heating rate. After this time, ageing-generated proto-nuclei are so numerous that the normal self-nucleation of the reaction mixture is suppressed and the product crystal size is independent of reaction conditions. There is a limit to the number of crystals which can be nucleated and this is an intrinsic property of the system.
0 2 - 0 - 0 3 - High yield synthesis of colloidal crystals of faujasite zeolites Qinghua Li, D. Creaser and J. Sterte
Division of Chemical Technology, Lule~t University of Technology, [email protected] A method for the preparation of colloidal zeolite Y in high yields is presented. Sodium was added to a colloidal zeolite Y synthesis mixture at varying times during the synthesis to increase the Na20/A1203 ratio to levels that normally favour the crystallization of zeolite A. A two-stage varying-temperature synthesis method was used to determine the nucleation period of colloidal zeolite Y. It was found that if sodium was gradually added after nucleation, instead of the formation of zeolite A, pure colloidal zeolite Y with a size of less than 120 nm and a more than six-fold increase in yield was obtained. The effect of the amount and the rate of Sodium addition during the crystallization on the formation of colloidal zeolite Y were also investigated.
141
0 2 - 0 - 0 4 - Colloid chemical properties of silicalite-I nanoslabs S. Kremer (a), C. Kirschhock (a), P. Rouxhet (b), P.A. Jacobs (a) and J.A. Martens (a)
Centrum voor Oppervlaktechemie en Katalyse, K.U. Leuven, Belgium johan, martens@agr, kule uven. ac. be. (b) Unitd de Chimie des Interfaces, Universitd Catholique de Louvain, Belgium Aggregation of Silicalite-1 nanoslabs in concentrated suspensions was studied. Nanoslabs have negative zeta potential and contain occluded and externally adsorbed TPA. At room temperature, the nanoslabs form physical aggregates, which dissociate upon dilution. The formation of these reversible aggregates accelerates Silicalite-1 synthesis upon heating. The influence on crystallisation of dilution with water or TPAOH solution and of salt addition may be explained by changes of the nanoslab mobility and of the nanoslab-nanoslab interfaces. The externally adsorbed TPA controls the formation of ordered chemical bonds between nanoslabs in contact and the subsequent crystal formation.
0 2 - 0 - 0 5 - A t o m i c force microscopy (AFM) used to relate surface topography growth m e c h a n i s m s in SSZ-42 M.W. Anderson (a), N. Hanif (a), J.R. Agger (a), C.-Y. Chen (b) and S.I. Zones (b)
a UMIST Centre for Microporous Materials, Manchester, [email protected], United Kingdom," b Chevron Research & Technology Co., Richmond, CA, USA This work details the atomic force microscopy of three faces of the microporous material SSZ-42. Interesting surface features have been observed on each face that are distinct and related to the structure of SSZ-42. These have been used to determine the crystal growth mechanism of SSZ-42. This study supports a layer growth mechanism whereby growth of crystals occurs at terrace sites and edges from nutrient in the solution and elucidate the templating mechanism.
11 - Post-Synthesis Modification (Monday pm)
11-O-01 - Gold-based mono- and bimetallic nanoparticles on H Y zeolites G. Riahi, D. Guillemot, M. Polisset-Thfoin, D. Bonnin and J. Fraissard
Laboratoire SIEN, Universitd Paris VI, Paris, polisset@ccr./ussieu.fr, France fax: 01.44.27.55.36 Stable nanoparticles of monometallic gold, or bimetallic Pd-Au and Pt-Au systems supported on Y-zeolite are obtained by an original method, in which the metallic precursors and the support play an important part in the formation and the stability of the particles. This method involves exchange of complexed cations with counter-ions of an acidified zeolite and their thermal reduction by the ligand (ethylenediamine) under inert gas flow. This preparation leads to nanometric mixed bimetallic particles. The particles have good stability at high temperature (500~ in dihydrogen or dioxygen.
142
11-O-02 - Unravelled from the back: kinetics of alkoxysilane CVD on zeolites and evidence for pore mouth plugging determined from model conversion over stepwise silanised samples H.P. ROger (a,b), H. Mantein (a), W. B6hringer (a), K.P. M611er (a) and C.T. O'Connor (a)
(a) Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, South Africa - [email protected]; (b) present address: Sad-Chemie AG, Division Catalysts, R&D, Bruckm~ihl, Germany Chemical vapor deposition (CVD) of tetraethoxysilane on HZSM5 was performed stepwise under well-controlled, mild conditions. Several test reactions were performed over the series of modified samples. Under mild conditions, CVD follows first order kinetics with respect to uncovered external sites on the zeolite crystals. The external surface is homogeneous with regard to both CVD and catalytic activity. Reactions, which are controlled by strong internal mass transfer restrictions, do respond in a way, which indicates that CVD causes pore mouth plugging rather than pore mouth narrowing.
11-O-03 - Templating role of F towards D4R units: transformation of the fluorogallophosphate Mu-3 into Mu-2
study
of the
A. Matijasic, P. Reinert, L. Josien, A. Simon and J. Patarin
Laboratoire de Mat~riaux Min~raux, UPRES-A 7016, ENSCMu, UHA, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France, [email protected] After a brief review on the templating role of F in the synthesis of molecular sieves, this study focuses on the transformation of Mu-3 into Mu-2, two fluorinated gallophosphates with 1D and 3D arrangement of fluorinated D4R units respectively. Depending on the water content and on the temperature, Mu-2 or another gallophosphate free of D4R units crystallizes. The transformation is studied by XRD analysis and NMR spectroscopy. The different results obtained show clearly that this transformation does not occur via a complete dissolution. Based on the 19F NMR spectra, the presence of a fluorinated D4R unit, in the solution, cannot be excluded.
1 1 - O - 0 4 - Modification of the Si/Ti ratio in E T S - 1 0 G. Koermer, A. Thangaraj and S. Kuznicki
Engelhard Corporation, Iselin, NJ 08830, USA, gerald, koermer@engelhard, corn ETS-10 is a thermally stable titanosilicate molecular sieve with potential for application in catalysis and adsorption. The as-synthesized Si/Ti ratio is 5. Methods for modification of the Si/Ti of ETS-10 are described. The resulting materials are characterized by elemental analysis, XRD, NMR, IR and raman techniques. These modified sieves show catalytic activity for oxidation of organic substrates with peroxide.
143
11-O-05 - Binuclear oxo-Fe species in Fe/ZSM-5 catalyst prepared by chemical vapour deposition P. Marturano a, L. Drozdovfi a, A. Kogelbauer b and R. Prins a
aLab. Tech. Chem., ETH-Z~irich, CH-8092 Ziirich, Switzerland (prins@tech. chem. ethz. ch) bDept. Chem. Eng. and Chem. Tech., Imperial College, London SW7 2BY, UK The existence of the binuclear oxo-iron species postulated in the literature for Fe/ZSM-5 was proved using EXFAS spectroscopy. The structural parameters obtained allowed to propose a model structure which closely resembles that of the active species of the methane monooxygenase enzyme ([Fe(~t-O)zFe] 2+ or [Fe(~t-O)(~t-OH)Fe]+). Magnetic susceptibility measurements (SQUID) further supported this conclusion, as they revealed the expected antiferromagnetic coupling between the Fe 3+ ions of the dimer. The electronic spectra also showed features attributable to such dimeric species. The hydrolysis occurring during the washing of the zeolite, after sublimation, was concluded to be the key step of the preparation.
1 8 - Adsorption and Separation Process (Mondaypm) 18-O-01 - An experimental adsorbent screening study for CO2 removal from flue gas P.J.E. Harlick, H. Halsall-Whitney and F. Handan Tezel*
Department of Chemical Engineering, University of Ottawa, Ottawa, Ontario, Canadatezel@eng, uottawa, ca The selection of a suitable zeolite adsorbent for C02 removal from flue gas (mixture of C02 and N2) has been carried out. The limiting heats of adsorption, Henry's Law constants for CO2 and N2, CO2 pure component adsorption isotherms and expected working capacity curves for Pressure Swing Adsorption (PSA) separation application were determined. The results show that the most promising adsorbent characteristics are a near linear CO2 isotherm and a low SIO2/A1203 ratio with a cation in the zeolite structure that has strong electrostatic interaction.
18-O-02 - Amino acids in BEA type channels C. Buttersack (a) and A. Perlberg (b)
a Institutfiir Technologie der Kohlenhydrate e. V., Braunschweig, Germany christoph, [email protected], b. Max-Planck-Institut Dynamik komplexer technischer Systeme, Magdeburg, [email protected] Germany Adsorption isotherms of amino acids in BEA type zeolites (SiO2/A1203 = 25 ...300, ionic form: H +, Na +, K +, Ca ++) have been analyzed. Phenylalanine, leucine, isolecine, methionine, and arginine were found to form dimers in the zeolite pores (SiOz/A1203 = 25, H +, Na + ). In case of higher content of silicium the dimerization was less pronounced. The adsorption was rather selective, depending on the pH and ionic form. Sorbate-zeolite interaction was essentially interpreted in terms of hydrophobic forces.
144
18-O-03 - Kinetic separation of binary mixtures of carbon dioxide and C2 hydrocarbons on modified LTA-type zeolites C.J. Guo, D. Shen and M. Btilow The BOC Gases Technology, Murray Hill, NJ 07974, USA; [email protected] A solution is offered to separate mixtures of carbon dioxide and C2-C4 hydrocarbons by enhancing equilibrium sorption selectivity via kinetic selectivity to achieve high overall separation efficiency. Basic Na-LTA type zeolite is modified gradually by ion exchange, K+ vs. Na+, to alter the effective cross-section of entrances to micropores of zeolite crystals. This leads to favorable differences between sorption uptake rates for carbon dioxide'and C2 hydrocarbons, viz., ethane, ethylene and acetylene. A challenging separation becomes practically viable by utilizing processes of pressure swing adsorption, PSA.
18-O-04 - A novel adsorbent for the separation of propane/propene mixtures w. Zhu, F. Kapteijn and J.A. Moulijn Section Industrial Catalysis, DelfiChemTech, Delft University of Technology, Julianalaan 136, 2628 BL Delft, w.zhu@tnv~:tudelft.nl, The Netherlands The adsorption of light hydrocarbons, such as ethane, ethene, propane, propene, and unsaturated linear C4 molecules, on the all-silica DD3R has been investigated using the tapered element oscillating microbalance, TEOM. Single component adsorption isotherms are reported at temperatures in the range from 303 to 473 K. Only minor differences exist between the adsorption of ethane and ethene. Transient adsorption experiments reveal that the eight-ring windows of the all-silica DD3R are accessible to propene, trans-but-2-ene, and buta-l,3-diene molecules, while they exclude propane, cis-but-2-ene, and but-l-ene molecules. The high shape selectivity for propene suggests that the all-silica DD3R might be effective as an adsorbent for the separation of propene and propane mixtures.
1 8 - O - 0 5 - Iodide removal using zeolite-based reactive adsorption S. Kulprathipanja and B. Spehlmann UOP LLC, 50 East Algonquin Road, Des Plaines, IL 60017-5017, USA UOP has developed Ag exchanged high silica to alumina ratio zeolite-Y adsorbents (e.g. Ag exchanged LZ-210) for the removal of both organic and inorganic iodide compounds from commercial acetic acid feed streams (1). Experimentally, good results were obtained with Ag exchanged LZ-210 having framework silica to alumina molar ratios of about 10-12. Specifically, laboratory breakthrough experiments demonstrated that Ag-LZ-210 removed methyl iodide, hexyl iodide, and hydrogen iodide from acetic acid having initially several hundred parts per million (ppm) by weight of total iodine to a level of 1 part per billion (ppb) in the effluent.
145
2 4 - New Routes to H y d r o c a r b o n Activation (Tuesday am) 24-O-01 - D e h y d r o i s o m e r i z a t i o n of n-butane to isobutene over Pd modified s i l i c o a l u m i n o p h o s p h a t e molecular sieves Y. Wei, G. Wang, Z. Liu, C. Sun and L. Xu
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, [email protected], China Several aluminophosphate molecular sieves with AEL topology structure were synthesized and modified by Pd for direct transformation reaction of n-butane to isobutene. The effect of pore geometry of the molecular sieves was studied. Pd modified 10-member ring SAPO-11 and metal-substituted A1PO-11 and SAPO-11 showed high selectivity towards isobutene. The incorporation of metal into the molecular sieves had effect on the product distribution. Catalytic properties and the result of chemical adsorption of monoxide predicted the interaction between the transition metal for substitution and the supported palladium.
2 4 - 0 - 0 2 - Conversion of methane over A g - Y in the presence of ethene T. Baba, H. Sawada, Y. Abe and Y. Ono
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, Japan. Ag-Y catalyzed the conversion of CH4 into higher hydrocarbons in the presence of C2H4. The conversions of CH4 and C2H4 were 6.3 % and 16.8 %, respectively at 673 K. Products were C2 - C5 hydrocarbons. The main product was C2H6, while the other hydrocarbon was mainly C3H6, which accounted for 28.8 mol% of the products. Both acidic proton and silver cations are essential for the activation of CH4 to from C3H6 by the reaction of CH4 with C2H4. HZSM-5 loaded with various cations such as Ag + also catalyzed the conversion of CH4 in the presence of C2H4. H-ZSM-5 loaded with Ag + showed the highest catalytic activity. The conversion of CH4 was 13.2% at 673 K, while C2H4 conversion was 86.3 %. Aromatics were mainly formed and the product composition was 30.3 mol%.
2 4 - 0 - 0 3 - Peculiarities in the hydroconversion bifunctional catalysts L. Perrotin a, A. Finiels a, F. Fajula a and T.Cholley b
of n - h e x a d e c a n e
over
a UMR 5618, ENSCMontpellier- CNRS, Montpellier, France," b TotalFinaElf Feluy, Belgique A kinetic study of n-hexadecane hydroconversion has been carried out over bifunctional catalysts prepared from EMT and FAU zeolites, MCM-41-type molecular sieves and amorphous silica alumina. A unique influence of hydrogen partial pressure characterized by a sharp optimum of activity at intermediate pressures has been revealed. A reaction model including the conventional bifunctional mechanism and the generation of active sites by hydrogen spillover is proposed to describe the experimental results.
146
2 4 - 0 - 0 4 - HI3 catalyzed heterogeneous aziridination of olefins B. Chanda a , R. Vyas a, A.V. Bedekar a, B.B. Kasture b and V.N. Joshi b
~Division of Organic Chemistry. Technology bCatalysis Division, NCL Pune, India. bhanu@dalton, ncl. res. in; bhanu.c'handa@yahoo, com A non-metal catalyzed synthesis of aziridines using HI3 zeolite under heterogeneous conditions was developed. The methodology gives aziridines in good yields and obviates the drawbacks of metal catalyzed aziridinations. Even the less reactive olefins like cinnamates underwent this reaction at ambient temperatures. Aliphatic, alicyclic and aromatic olefins all undergo the transformation. An interesting feature of the conversion of olefins is the selective formation of trans isomer. Under metal catalyzed homogenous conditions the same substrates give cis/trans mixtures. It has been speculated that the reaction takes place inside the pore of the cavity of the zeolite which is large enough for the aziridine molecule to fit into. In order to demonstrate this, molecular modelling studies were carried out on both the isomers using PCMODEL software.
24-0-05 - MCM-41 polymerization
as support
for
metailocene
catalysts
- ethylene
C.A. Henriques a, M.F.V. Marques b, S. Valange c, Z. Gabelica d and J.L.F. Monteiro e alnstituto de Quimica/UERJ, RJ, Brasil," blnstituto de Macromoldculas Prof. Eloisa Mano/UFRJ, RJ, Brasil; c ESIP, Poitiers, France," dENSCMu, GSEC; Mulhouse, France," eNUCA T - COPPE/UFRJ, monteiro@peq, coppe, ufrj. br, RJ, Brasil Al-containing (A1MCM) and all-silica (SiMCM) MCM-41 were evaluated as supports for Cp2ZrCI2 as a catalyst for C2H4 polymerization. While SiMCM without pre-treatment with metallocene/methylaluminoxane (MAO) did not fix the metallocene in a catalytically active form, as also observed for a commercial silica sample, Cp2ZrC12 supported on MAO-free A1MCM yielded polymers with narrow polydispersity and the highest molecular weight of the series, although with a low activity. All the MAO pre-treated supports originated catalysts that exhibited activities comparable to those of homogeneous zirconocenes.
01 - Mineralogy of Natural Zeolite (Tuesday am) OI-K-OI - Pentasil zeolites from Antarctica: from mineralogy to zeolite science and technology A. Alberti a, G. Cruciani a, E. Galli b, S. Merlino c, R. Millini d, S. Quartieri ~, G.Vezzaliniband S. Zanardi a
~Universitit di Ferrara, Italy, [email protected]; bUniversit~t di Modena e Reggio Emilia, Italy." CUniversit~t di Pisa, Italy. dEniTecnologie S.p.A., S. Donato Milanese, Italy. eUniversit~l di Messina, Italy This paper deals with chemical and crystallographic properties of new and very rare zeolites found at Mt. Adamson (Northern Victoria Land, Antarctica). These are gottardiite, mutinaite and tschernichite, the natural counterparts of synthetic NU-87, ZSM-5 and beta, respectively, and terranovaite and boggsite, whose frameworks are unknown among synthetic materials. Mineral properties are compared with those of the synthetic analogues.
147
01-O-02Natural zeolites mineralization in the Oligocene-Miocene volcano-sedimentary succession of Central Sardinia (Italy) P. Cappellettia, G. Cerria, M. de ~ a ,
A. LangeUab, S. Naitzac, G. PadalinoC,M. Palomba~and R, Rizzoc
aDipartimento di Scienze della Terra, Universith di Napoli Federico II, Napoli, Italy bFacolt~t di Scienze, Universith del Sannio, Benevento, Italy CDipartimento di Geoingegneria e Tecnologie Ambientali, Universit~ di Cagliari, Cagliari, Italy dCentro Studi Geominerari e Mineralurgici del CNR, Universit~t di Cagliari, Cagliari, Italy Investigations performed on the Cenozoic volcano-sedimentary sequence of Central Sardinia recognized widespread secondary mineralization processes, differently affecting the volcanic and sedimentary units cropping out in the region. Mineralogical studies evidence zeolite mineral association consisting of clinoptilolite and mordenite, locally attaining economic concentrations. Chemical composition of mordenite and clinoptilolite is strongly correlated with the rhyodacitic glassy precursor. Secondary mineralization process which affected the volcaniclastic and epiclastic deposits, enables to identify the most interesting areas, as far as zeolite grade is concerned. Up to now, available data are not sufficient for an exhaustive definition of the complex and articulated minerogenetic processes which originated the zeolitization.
01-O-03 - Cation location and its influence on the stability of clinoptilolite *M.N. Johnson, *G. Sankar, *C.R.A. Catlow, **D. O'Connor, **P. Barnes and +D. Price.
*Royal Institution of Great Britain, London, UK. [email protected] **Birkbeck College, Crystallography Dept., London, +University College London, Geology Dept., London, UK Clinoptilolite is used as a medium for storage of low grade nuclear waste. Here we present data collected on the Energy Dispersive X-ray Diffraction (EDXRD) station 16.4 at Daresbury Synchrotron Radiation Source, UK, that clearly identifies the effects of various ion exchanged cations upon the structural stability of clinoptilolite. This data is the beginning of a much larger project that potentially will increase the sorption capabilities and storage potential of clinoptilolite for safer storage of nuclear waste.
0 1 - O - 0 4 - The structure of Li-phillipsite A.F. Gualtieri
Dipartimento di Scienze della Terra, Universitgt di Modena e Reggio Emilia, Italy, [email protected] This work describes the results of the Rietveld structure refinement of a Li-exchanged natural phillipsite in the frame of a long term project on the crystal chemistry and properties of exchanged phillipsites. A natural phillipsite from Vallerano (Rome, Italy) with a Si/(Si+A1) ratio of 0.63 was exchanged with Li + and its structure was refined with the Rietveld method using conventional powder diffraction data. The structure has K + and water in site I and Na + and Ca ++ in site II. Li + was refined in site II' with a population of 100% and a tetrahedral coordination with 2 framework oxygens and 2 water molecules at an average distance of 1.961 A. The assignment of the Li + position was possible by considering the short cationanion distances.
148
01-O-05 phillipsite
Ion-exchange
features
of
intermediate-silica
sedimentary
C. Colella l, E. Torracca 2, A. Colella 3, B. de Gennaro I I). Caputo I and M. de Gennaro 3
I Universit~ Federico II, Napoli, Italy," 2Universith Roma 3, Roma, Italy," 3Universit~ Federico II, Napoli, Italy Equilibrium ion-exchange data for intermediate-silica Na-exchanged phillipsite at 25~ in the presence of cation pairs Na/X, where X is Ba, Co, NH4, K or Ca, were collected and the relevant thermodynamic parameters were computed. Phillipsite was found very selective for Ba, K and NH4, unselective for Co, whereas only about 50% Na could be readily replaced by Ca. This behaviour was interpreted in terms of phillipsite's structural features. On the basis of the present and the previous data concerning other cations, possible applications of alkalitrachytic phillipsite-rich rocks could be envisaged in the treatment of wastewaters containing Ba, Cs, Pb and/or NH4, especially if the waters are lacking K as an interfering cation.
1 5 - Modelling and Theoritical Studies A (Tuesday am) 15-O-01 - Proton jumps in dehydrated predictions based on ab-initio calculations
acidic zeolite catalysts. Rate
M. Sierka and J. Sauer*
Humboldt-Universitat zu Berlin, Institut fiir Chemie, Berlin, Germany On-site proton jumps between neighboring oxygen atoms of the A104 tetrahedron in proton forms of CHA, FAU, and MFI zeolites are studied. Comparison is made with inter-site jumps to neighboring Si-O-Si bridges. In H-MFI the barrier for leaving the AIO4 tetrahedron is 132 kJ/mol. The barriers for on-site jumps are between 52 and 106 kJ. While in all three zeolites both low and high barriers exist, different structural features of the three frameworks suggest that the proton mobility is generally lower in chabazite and faujasite than in ZSM-5, in agreement with NMR results. The calculations of the energy barriers employ the QM-Pot method. At room temperature the calculated rates vary over a broad range of 10-6 to 105 s"~. Proton tunneling effects appear to be negligible above room temperature.
1 5 - O - 0 2 - A b - i n i t i o simulation of dynamical processes in zeolites L. Benco (a), T. Demuth (a), J. Hafner (a), F. Hutschka (b) and H. Toulhoat (c)
alnstitut fuer Materialphysik and Center for Comput. Mater. Science, Wien, Austria, [email protected], bTotal Raffinage Distribution, Centre Europden de Recherche et Technique, Harfleur, France, Clnstitut Frangais du Pdtrole, Rueil-Malmaison Cedex, France Ab-initio density-functional molecular dynamics is used to characterize dynamical processes in zeolites. Simulations performed on the structure of gmelinite show that the proton transfer between the O-sites is a spontaneous process enabled in both Na-free and Na-zeolite by just one water molecule adsorbed to the acid site. A proton attack of the acid zeolite at the hydrocarbon molecule is investigated at increased temperature of 700 K. In the protonated molecule a series of proton jumps are observed indicating their high mobility.
149
15-O-03 - A theoretical study of the methylation of toluene by methanol over acid mordenite A. Vos (a), X. Rozanska (b), R. Schoonheydt (a), R. van Santen (b), F. Hutschka (c) and J. Hafner (d)
a Centrum voor Oppervlaktechemie en Katalyse, Katholieke Universiteit Leuven, Belgium b Schuit Institute of Catalysis, Eindhoven University of Technology, The Netherlands c TotalFina, Centre Europden de Recherche et Technique, Harfleur, France d Institutfiir Materialphysik, Universitcit Wien, Austria A theoretical study of the alkylation of toluene by methanol catalysed over acid mordenite is presented. Cluster DFT as well as periodic structure DFT calculations have been performed to obtain full reaction energy diagrams of the elementary reaction steps leading to the formation of the three xylene isomers. The use of periodic structure calculations allows to take into account the framework electrostatic contributions and steric constraints that are important in zeolite catalysis. 1 5 - O - 0 4 - Coverage effects on adsorption of water in faujasite: an ab-initio cluster and embedded cluster study J. Limtrakul, S. Nokbin, P. Chuichay, P. Khongpracha, S. Jungsuttiwong and T. N. Truong
Laboratory for Computational & Applied Chemistry, Chemistry Department, Kasetsart University, Bangkok 10900, Thailand, e-mail."[email protected] The influence of high coverages of adsorbing molecules on zeolites has been investigated by means of both the density functional theory quantum cluster and the embedded cluster methods. For cluster models, equilibrium structures determined for the adsorbing molecules successively added from one to four molecules per acid site. While [H3SiOAI (OH)zSiH3]/[H20] and [H3SiOAI(OH)2SiH3]/[H20]2 are a hydrogen-bonded complex, cluster of [H3SiOAI(OH)2SiH3]/[H20]4 they contain both types of ion-pair and neutral complexes. It is shown that for the zeolite/(H20)3 complex, a complete proton transfer, ZO(H30+)(H20)2, can be observed when the zeolite lattice potential is taken in to account.
The Beckmann rearrangement catalyzed by silicalite: a spectroscopic and computational study G.A. Fois a, G. Ricchiardi a, S. Bordiga a, C. Busco a, L. Dalloro b, G. Span6 b and A. Zecchina b 15-O-05-
a Dipartimento di Chimica IFM, Via P. Giuria 7, 1-10125 Torino, Italy, [email protected]. it; b EniChem S.p.A., Centro Ricerche Novara, "Istituto Guido Donegani The rearrangement of cyclohexanone oxime to caprolactam over zeolites with MFI and FAU structure is investigated by means of spectroscopical (IR) and computational methods. Hydrogen bond interactions, proton transfer and rearrangement are detected. The thermal reaction mechanism and that catalyzed by H + are studied with QM methods of B3LYP/631 +G(d,p) quality. The same reaction path in presence of HC1 and silanol is studied in order to model acids of different strength. The H+-catalyzed mechanism is found to be a multi-step mechanism in which proton transfer from N to O in the oxime is the rate determining step. With weaker acids, a single-step mechanism is found.
150
0 7 - New Mesoporous Molecular Sieves (Tuesdayam) 07-O-01 - Ordered mesoporous carbon molecular sieves by templated synthesis" the structural varieties R. Ryoo (a)*, S.H. Joo (a), S. Jun (a), T. Tsubakiyama (b) and O. Terasaki (b,c)
a Korea Advanced Institute of Science and Technology, Taejon, Korea, [email protected], b Department of Physics and CIR, Tohoku University, Sendai, Japan c CREST, JST Corporation, Tohoku University, Sendai 980-8578, Japan Ordered mesoporous carbons (OMC) of various structures, designated as CMK-1-5, have been synthesized by carbonization of sucrose, furfuryl alcohol or other carbon sources inside silica or aluminosilicate mesopores that are interconnected into three-dimensional networks such as in MCM-48, SBA-1 and SBA-15. The mesoporous carbon molecular sieves, obtained after template removal, show TEM images and XRD patterns characteristic of the ordered arrangement of uniform mesopores. The OMC, which are opening up a new area of the nanoporous materials, exhibit high BET specific surface areas, excellent thermal stability in inert atmospheres and strong resistance to attack by acids and bases.
0 7 - 0 - 0 2 - One-pot synthesis of phenyl functionalized porous silicates with hexagonal and cubic symmetries V. Goletto (a), M. Imp6ror (b) and F. Babonneau (a) a Chirnie de la Mati~re Condensde, UPMC, Paris; b Universitd Paris-Sud, Orsay, France Phenyl functionalized silicates with cubic Pm3n and 2D p6m symmetries have been prepared by direct reaction of a mixture of phenyltriethoxysilane and tetraethoxysilane with an aqueous solution of cetyltrimethylammonium bromide, under acidic or basic conditions. Their structural characterization by XRD using synchrotron radiation, multinuclear MAS-NMR (including 2-dimensional 1H homonuclear correlation) and N2 adsorption-desorption isotherms will be reported in order to better describe the localization of the phenyl groups in the silicate framework.
0 7 - 0 - 0 3 - State and redox behavior of iron in MCM-41 G. P~l-Borb61ya, A. Szegedi a, K. L~zfirb and H.K. Beyer a
a Institute of Chemistry, Chemical Research Center, Hungary, [email protected] b Institute of Isotope and Surface Chemistry, Chemical Research Center, Hungary Mesoporous Fe-MCM41 samples with different framework iron contents were synthesized and characterized by TPR, in situ FTIR and M6ssbauer spectroscopy after thermal pretreatments in high vacuum (autoreduction) and treatments in reductive (CO) and oxidative (O2/He) atmospheres. Changes in the coordination and oxidation state of iron in Fe-MCM41 subjected to successive redox treatments were detected by both spectroscopic methods. At higher temperatures (720 K) all iron proved to be reversibly involved in Fe(III)~--~Fe(II) redox cycles. The results are interpreted in terms of structural features of iron species isomorphically incorporated into MCM41. A reaction mechanism involving the formation of framework oxygen vacancies during reduction and restoration of the structure upon reoxidation is proposed for the redox process.
151
0 7 - 0 - 0 4 - A comparative study of Cu interaction with niobium- and aluminium-containing MCM-41 molecular sieves M. Ziolek a, I. Sobczak a, I. Nowak a, P. Decyk a and J. Stoch b
m. University, Poznan, Poland, [email protected], b Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Cracow, Poland
aA
The interaction between Cu and Nb in the mesoporous molecular sieves of MCM-41 type has been studied. The results were compared with those found for copper containing aluminosilica sieves (A1MCM-41). Cu cations in NbMCM-41 matrix are slightly reduced during heating at 723 K under a low vacuum and deeply (<+1) under a high vacuum, whereas, in A1MCM-41 copper is partially reduced to Cu + under a high vacuum. The results of the reaction between copper and the extra framework niobium species are discussed. The strong interaction of copper species with niobium, introduced into the framework of the molecular sieves, determines the catalytic properties of the materials.
07-0-05 - A novel synthesis strategy leading to the formation of stable transition-metal-oxide mesostructures X.S. Zhao (a), J. Drennan (b) and G.Q. Lu (a)
a Nanomaterials Center and Department of Chemical Engineering, b Center for Microscopy and Microanalysis, The University of Queensland, [email protected], Australia. This paper describes a new synthesis strategy of preparing thermally stable mesostructured transition metal oxides, namely, two-step synthesis (TSS). Basically, the synthesis course involves two steps: (1) formation of a mesostructured transition metal oxide solid mediated by surfactant in a basic aqueous solution; and (2) treatment of the solid product in an acidic organic solvent containing the respective precursor from which the solid product was produced. The final material synthesized according to such a method is thermally stable and structurally mesoporous with high surface area and uniform pores arranged disorderedly. 25 - Conversion of Aromatics (Tuesday pm)
25-O-01 - Shape-selective methylation of 4-methybiphenyl dimethybiphenyl over modified ZSM-5 catalysts
into 4,4'-
J.-P. Shen, L. Sun and C. Song
Clean Fuels and Catalysis Program, The Energy Institute, and Department of Energy & GeoEnvironmental Engineering, The Pennsylvania State University, USA, [email protected] A linear polycyclic compound, 4,4'-dimethylbiphenyl (4,4'-DMBP), is an intermediate for making monomer of some advanced polymer materials, but the selective synthesis of 4,4'DMBP is difficult. In this work, modifications were made on a ZSM-5 zeolite for selective methylation of 4-methybiphenyl (4-MBP) to form 4,4'-DMBP. The use of binder, deposition of basic oxide such as calcium oxide over zeolite internal and external surface can effectively improve the product selectivity. An isomorphous substitution of ZSM-5 framework AI with Fe by a post-synthetic treatment, coupled with modification of external and internal surface by P or Ca leads to high-performance catalyst with stable activity and superior selectivity for synthesis of 4,4'-DMBP by 4-MBP methylation.
152
25-0-02 - Facile Friedei-Craft's alkylation of phenol with 4-hydroxybutan2-one over 13 and Y zeolites to produce raspberry ketone K.K. Cheralathan, I.S. Kumar, B. Arabindoo, M. Palanichamy and V. Murugesan* Department of Chemistry, Anna University, Chennai, India- v [email protected] Friedel-Craft's alkylation of phenol with 4-hydroxybutan-2-one was investigated over HI3, HY and Zn 2+ and Fe 3+ ion exchanged [3 and Y zeolites. The expected para-alkylated product raspberry ketone [4-(4-hydroxyphenyl)butan-2-one] was obtained regioselectively over HI3 (SIO2/A1203=10) catalyst in 77% yield. The para product is formed not only by direct alkylation but also by the facile rearrangement of O-alkylated product. HY and cation exchanged catalysts yielded O-alkylated, para-alkylated and small amount of ortho-alkylated products.
2 5 - 0 - 0 3 - Selective alkylation of naphthalene to 2,6-dimethylnaphthalene catalyzed by M T W zeolite G. Pazzuconi a, G. Terzoni b, C. Perego a and G. Bellussi a a EniTecnologie S.p.A., San Donato Milanese, [email protected], Italy b EniChem S.p.A., San Donato Milanese, Italy The methylation of naphthalene and methylnaphthalene with zeolitic catalysts was studied. The main purpose was to achieve a selective synthesis of 2,6-dimethylnaphthalene (2,6-dmn). The alkylation of naphthalene with methanol didn't give interesting results. Best performances were obtained with 1,2,4-trimethylbenzene as solvent/reagent, together with methanol. In such chemical system, among several medium and large pore zeolites, MTW stands out for both activity and selectivity to 2,6-dmn. As transalkylation is the main reaction, this behavior can be explained if a restricted transition state shape selectivity takes place.
2 5 - 0 - 0 4 - Transalkylation reaction of phenol with trimethylbenzenes over Y and EMT zeolites V. Hulea (a), I. Fechete (a), P. Caullet (c), H. Kessler (c), T. Hulea (a), C. Chelaru (b), C. Guimon (d) and E. Dumitriu (a) a Iasi Technical University, Iasi, [email protected]~ Romania; b Institute of Macromolecular Chemistry, Iasi, Romania; c Ecole Nationale Sup~rieure de Chimie de Mulhouse, France ; d Laboratoire de Physico-Chimie MoHculaire, Pau, France The catalytic properties of dealuminated Y and EMT-type zeolites for the vapor phase transalkylation reaction of phenol with the trimethylbenzenes were investigated. The influence of the reaction temperature, the degree of dealumination and the concentration of acid sites, and the nature of the TMB isomer, were taken into account. High catalytic performances (activity and selectivity to cresols) and good resistance to coking of the dealuminated zeolites were observed.
153
2 5 - 0 - 0 5 - Benzene alkylation with alkanes over modified MFI catalysts A.V. Smirnov, E.V. Mazin, O.A. Ponomoreva, E.E. Knyazeva, S.N. Nesterenko and I.I. Ivanova*
Chemistry Department, Moscow State University, [email protected] Benzene alkylation with ethane, propane and i-butane has been studied on acidic H-MFI zeolite with SIO2/A1203 ratio of 104; mixed (H-MFI + Pt/CeO2) catalytic systems and Pt/HMFI bifunctional catalysts with Pt content of 0.3 %. In some of the experiments, hydrideforming metals (M) were added to the catalytic systems to ensure H2 removal from the reaction zone. The conversion of alkanes and the selectivity to the products of direct addition was found to increase in the following order of catalytic systems: H-MFI < (H-MFI + Pt/CeO2) < Pt/H-MFI < (Pt/H-MFI + M). The reactivity of alkanes increased in the following order of reactants: C2H6 < C3H8 < C4HI0; while their alkylating ability was found to increase in the reverse order.
1 9 - Diffusion: Fundamentals Approach (Tuesdaypm) 19-K-01 - Use of ~H N M R imaging to study the diffusion and co-diffusion of gaseous hydrocarbons in H Z S M - 5 catalysts P. N'Gokoli-Kekele (a), M.-A. Springuel-Huet (a), J.-L. Bonardet (a), J.-M. Dereppe (b) and J. Fraissard (a)
~Laboratoire S.I.E.N, Universit6 P. et M. Curie, Paris, [email protected], France 6Laboratoire de Chimie-Physique et Cristallographie, Universit6 Catholique de Louvain-laNeuve, Belgium IH NMR imaging has been used to study the diffusion of pure hydrocarbons (benzene, nhexane,) during their adsorption in or desorption from a fixed bed of zeolite crystallites. This technique is used to visualize the progression of the diffusing molecules in the zeolite bed and to determine their intracrystallite diffusion coefficients. In the case of competitive adsorption, it gives the time dependence of the distribution of the two coadsorbed gases.
19-O-02 - Studies of adsorption, diffusion and molecular simulation of cyclic hydrocarbons in MFI zeolites L. Song (a), Z.L. Sun (b) and L.V.C. Rees (a,*)
a Chemistry Department, University of Edinburgh, West Mains Road, Edinburgh EH93JJ, UK, [email protected]; b Applied Chemistry Department, Fushun Petroleum Institute, Fushun, Liaoning, 113001, P.R. China The adsorption and diffusion of C6-C8 aromatics and alkylcyclohexanes in MFI zeolites have been investigated systematically using a gravimetric balance and the frequency-response (FR) technique respectively. The packing arrangements patterns of these sorbate molecules in silicalite-1 at different loadings were also simulated using the Solid_Docking software package in InsightII, which combined MD, MC and EM techniques, developed by MSI. The configurations derived from the calculations are shown in detail.
154
19-O-03 - The effect of silanisation on the intraerystalline diffusivity of ZSM-5 W.L. Duncan and K.P. M611er
University of Cape Town, South Africa [email protected] Deposition of silane on a zeolite's external surface is a well-established method of increasing its shape selective properties by increasing diffusion resistances. In this work, the intracrystalline diffusivities of both parent and silanised ZSM-5 samples are measured by the zero length column technique. It is found that the apparent intracrystalline diffusivity does decrease in the modified samples. This change'is either the result of a surface barrier caused by pore mouth narrowing or an increase in intracrystalline tortuosity as a result of pore blockage. It was attempted to clarify the dominant mechanism by considering various mathematical models.
19-O-04 - Interference microscopy as a tool of choice for investigating the role of crystal morphology in diffusion studies O. Geier l, S. Vasenkov l, E. Lehmannl, j. K/~rgerl, R.A. Rakoczy 2 and J. Weitkamp 2
t Universitcit Leipzig, kaerger@physik, uni-leipzig.de; 2Universitgit Stuttgart, Germany Interference microscopy is applied to carry out investigations of the influence of the regular intergrowth effects commonly observed in large silicalite crystals on adsorption/desorption of adsorbate molecules. The intracrystaline concentration profiles measured by the interference microscopy during adsorption of isobutane are compared with those simulated using the Monte Carlo method. The comparison of the simulated and the measured profiles allows to rule out the uptake of isobutane from gas phase into silicalite crystals directly through the internal interfaces separating the intergrowth sections of the crystals.
1 9 - O - 0 5 - Estimation of the interphase thickness and permeability in polymer-zeolite mixed matrix membranes A. Erdem-$enatalar, M. Tather and ~.B. Tantekin-Ersolmaz
Istanbul Technical University, Maslak, Istanbul, ([email protected]), Turkey A method for determining the effect of particle size on the effective permeability values of zeolite-polymer mixed matrix membranes has been developed in this study. The model presented is a modified form of the effective medium theory, including the permeability and thickness of an additional phase, the interphase, which is assumed to surround the zeolite particles in the polymer environment. The interphase thickness and permeability values were determined by taking into consideration the assumptions that in case the size of the zeolite particles is held constant, the interphase thickness should be equal for different gases and in case the zeolite particle size is varied, the interphase permeability should remain constant for the same gas. The model seems to fit the experimental permeability data for O2, N2 and CO2 in the silicalite-PDMS mixed matrix membranes well.
155
1 6 - Modelling and Theoritical Studies B (Tuesday pm) 16-O-01 Simulating shape selectivity in alkane hydroconversion by zeolites M. Schenk a, T.L.M. Maesen b and B. Smit a
aDepartment of Chemical Engineering, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WVAmsterdam, The Netherlands bChevron Research and Technology Company, Richmond, CA, USA Using configurational-bias Monte Carlo simulations we quantify how molecular sieves shape selectively modify the free energy of formation of adsorbed hydrocarbons. This allows for a basic thermodynamic analysis to explain the differences in alkane hydroconversion between MFI- and MEL-type molecular sieves, and regularities in the alkane yields of TON-type molecular sieves.
16-O-02- Molecular dynamics of the faujasite (111) surface B. Slater and C.R.A. Catlow
Davy-Faraday Research Laboratory, The Royal Institution of Great Britain, [email protected], United Kingdom We report classical molecular dynamics results for the most stable faujasite surface, which dominates in the crystalline morphology. The changes that occur at external apertures (which provide access to the crystal interior/exterior for select molecules) at ambient temperatures are interpreted in the context of recent calculations on the adsorption of benzene at this surface.
16-O-03 - Adsorption of xylene isomers and water in faujasites. A molecular simulation study S. Buttefey, A. Boutin and A.H. Fuchs
Laboratoire de Chimie Physique, Orsay, France, [email protected] /k Grand canonical ensemble Monte Carlo simulations of the adsorption properties of several model faujasite zeolites were performed using the statistical bias method. The results enable a better understanding of the effect of cation exchange in the selective adsorption of binary mixtures of para and meta xylene isomers. We predict that adding a small amount of water molecules could enhance the adsorption selectivity in favour of p-xylene.
156
16-O-04 - Reaction dynamics in acidic zeolites: room t e m p e r a t u r e tunneling effects J.T. Fermann and S.M. Auerbach University of Massachussets, Amherst, MA 01003 (fermann@chem. umass, edu) We present recommendations for accurately and efficiently calculating transition state parameters for proton transfer reactions in zeolites. DFT with the B3LYP functional gives accurate structures and vibrational frequencies. MP2 energies in larger basis sets are augmented with MP4 energies in more limited basis sets to yield accurate classical barrier heights. Even after correcting for the effect of long range interactions, our barrier heights are significantly larger than those reported in the experimental literature. By evaluating proton transfer rate coefficients using semiclassical transition state theory, we attribute the discrepancy to neglect of tunneling in the interpretation of experimental data.
16-O-05 - M o l e c u l a r modeling of m u l t i c o m p o n e n t diffusion in zeolites and zeolite m e m b r a n e s M.J. Sanborn, A. Gupta, L.A. Clark and R.Q. Snurr Department of Chemical Engineering, Northwestern University, Evanston, IL 60208 USA Molecular dynamics (MD) simulations have been used to simulate non-equilibrium binary diffusion in zeolites. Highly anisotropic diffusion in boggsite provides evidence in support of "molecular traffic control." For mixtures in faujasite, Fickian, or transport, diffusivities have been obtained from equilibrium MD through appropriate correlation functions and used in macroscopic models to predict fluxes through zeolite membranes under co- and counterdiffusion conditions. For some systems, MD cannot access the relevant time scales for diffusion, and more appropriate simulation techniques are being developed.
0 5 - Synthesis of N e w Materials (Tuesdaypm) 05-O-01 - SOMS: Sandia octahedral molecular sieves. A new class of ion e x c h a n g e r s selective for the removal of Sr 2+ from waste streams T.M. Nenoff a, M. Nyman a, A. Tripathi b, J.B. Parise b,c, W.T.A. Harrison d and R.S. Maxwell e a Sandia National Labs, Alb., NM 87185-0755, USA, [email protected] b Dept. ofGeosciences, CDept. of Chemistry; SUNY-.Stony Brook, NY 11790, USA d Dept. of Chemistry, University ofAberdeen, UK; e LLNL, Livermore, CA 94551, USA We report on a new class of Sandia Octahedral Molecular Sieves (SOMS). The niobate-based sieves have a Na/MmV/Nb (M = Ti, Zr) oxide framework, with variable MlV:Nb (1:50-1:4) ratios, exchangeable Na cations and H20 in open channels. Synchrotron X-ray, NMR, thermal and elemental analyses were combined to solve the structure of SOMS-I" Na16Ti3.2Nb12.8044.8 (OH)3.2o8H20. SOMS have extreme selectivity for divalent cations. The ion-exchanged SOMS undergo direct thermal conversion to perovskite-type phases, indicating a promising new method for removal and immobilization of radioactive Sr-90 and industrial RCRA metals.
157
0 5 - 0 - 0 2 - Hydrothermal synthesis of various titanium phosphates in the presence of organic amine templates Yunling Liu, Yunlong Fu, Jiesheng Chen, Yongcun Zou and Wenqin Pang*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, P R. China. E-mail. [email protected] By varying the amine used as a structure-directing agent, the reaction temperature and the composition of the reaction mixture, a number of titanium phosphates (TiPO4-Cn, n=l-13) with a new structure have been obtained. The products were characterized by means of X-ray diffraction, scanning electron microscopy, IR spectroscopy, inductively coupled plasma characterization, thermogravimetric and differential thermal analyses and single crystal structure characterization. Structural characterization indicates that TiPO4-Cn crystals are invariably composed of octahedral TiO6 and tetrahedral PO4 units.
0 5 - 0 - 0 3 - On the role of azamacrocycles and metal cations in the syntheses of metalloaluminophosphates STA-6, -7 and - 8 R. Garcia, a E.F. Philp, a A.M.Z. Slawin, a P.A. Wright a'* and P.A. Cox b
School of Chemistry, The University of St. Andrews, UK, [email protected] b Centrefor Molecular Design, University of Portsmouth,, Hants, UK a
The azaoxamacrocycle 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (K22) and the azamacrocycle 1,4,8,11-tetramethyl-l,4,8,11-tetraaza-cyclotetradecane (tmtact) act as structure directing agents in the hydrothermal crystallisation of metalloaluminophosphates (MAPO's). K22 templates a CoAPO (STA-8) with the MSO framework topology. The crystalline products using tmtact depend strongly on the metal cations added. Nickel and rhodium may be incorporated, complexed by the macrocycle, within STA-6 and STA-7.
05-O-04 - Chiral transference and Co(en)3Cl3-templated zinc phosphates
molecular
recognition
in
novel
Jihong Yu, Yu Wang, Zhan Shi and Ruren Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, [email protected], People's Republic of China Two novel zinc phosphates, [ZngP6024C1][Co(en)3]'2H20 (I) with 3-dimensional openframework structure and [Zn6PsO32Hs]'2[Co(en)3] (II) with 2-dimensional layered structure, have been hydrothermally prepared using a racemic Co(en)3C13 complex as the template and structurally determined by single-crystal X-ray diffraction. This work gives a nice example of how recognition phenomena between an organometallic chiral guest and an inorganic host framework or network can lead to crystallization of structures that retain the chiral character of the guest.
158
0 5 - 0 - 0 5 - Very open microporous materials: from concept to reality A.K. Cheetham(c), H. Fjellvfig(a), T.E. Gier(b), K.O. Kongshaug(a), K.P. Lillerud(a*) and G. D. Stucky(b)
a Chemistry, University ofOslo, P.O Box 1033 Blindern, N-0315 Oslo, Norway bDepartment of Chemistry, University of California, Santa Barbara, CA 93106, USA cMaterials Research Laboratory, University of California, Santa Barbara, CA 93106, USA Two new zeolite topologies named, OsloSantaBarbara-1 and -2 are presented. These structures are base on 3-ring architectures. OSB-1 is the first example of a zeolite topology constructed from 3-rings only, The 14-ring channels are chiral and formed by a double helix chain out of 3-rings. The OSB-2 structure possess the most open, non interrupted, frame-work ever, FDsi OSB-2 = 12.7. OSB-1 has the same low FDsi as FAU.
26 - Catalysis for Oil Refining (Wednesday am) 26-O-01 - The isomerization selectivity in F C C process L.-J. Yan, M.-Y. He, J. Fu and J. Long
Research Institute of Petroleum Processing, [email protected], P R China The chain mechanism of n-hexane cracking has been studied. A parameter "cracking chain length" (CCL) has been proposed and used to correlate with bi-molecular reactions and isomerization selectivity. The effects of zeolite structure on the mechanism of n-hexane cracking and CCL have been studied. Catalyst design is based on the understanding of the chain mechanism of the cracking reactions and the correlation between CCL and zeolite properties. A new series of catalysts GOR has been developed and commercially applied in a number of FCC units.
2 6 - 0 - 0 2 - Design of zeolite catalyst for paraffin isomerisation J. Hou~vi6ka, C.J.H. Jacobsen and I. Schmidt
Haldor Topsoe A/S, Lyngby, Denmark Mesoporous zeolites are novel materials. They consist of large, single crystals, each with an 2 internal mesopore system with specific surface areas above 100 m / g . These mesoporous zeolites are more active isomerisation catalysts than ordinary zeolites of a similar composition, this being ascribed to lower diffusion limitations, particularly in the case of longer paraffins and narrow pore zeolites. The higher activity is achieved by the large number of active sites in the pore mouths which are easily accessible via the mesopores. External OHgroups are too weak acids to be active in isomerisation. This conclusion is reached as the selectivity pattern remains unchanged despite the very large external surface area.
159
2 6 - 0 - 0 3 - Cyciohexane ring opening on metal-zeolite catalysts T.V. Vasina (a), O.V. Masloboishchikova (a), E.G. Khelkovskaya-Sergeeva (a), L.M. Kustov(a) and P. Zeuthen (b)
(a) N.D.Zelinsky Institute of Organic Chemistry, Moscow, Russia- [email protected] (b) Haldor Topsoe A/S, Lyngby, Denmark Various zeolite catalysts (H-ZSM-5, H-MOR, H-Beta, La-FAU) modified with noble metals (Pt, Pd, Rh, Ru) were tested in ring opening of cyclohexane. Methylcyclopentane, gas products (CI-C4), n-hexane, and isohexanes were shown to be the main reaction products. The highest ring opening selectivity was found for Pt/H-ZSM-5, Rh/H-ZSM-5, and Pt/H-Beta catalysts. The metals reveal the following order of ring-opening activity: Pt ~ Rh > Pd >> Ru ~ Ni. Acidity was found to be important for achieving reasonable activity in ring opening of cyclohexane and simultaneous isomerization into methylcyclopentane and isohexanes.
2 6 - 0 - 0 4 - Selective ring opening of naphthenic molecules M. Daage, G.B. Mc Vicker, M.S. Touvelle, C.W. Hudson, D.P. Klein, B.R. Cook, J.G. Chen, S. Hantzer, D.E.W. Vaughan and E.S. Ellis
ExxonMobil Research and Engineering, USA Selective Ring Opening (SRO) requires that only one C-C bond internal to each naphthene ring is broken thereby preventing molecular weight reduction. Alkylcylopentanes (RC5) SRO can be readily achieved by hydrogenolysis on noble metal catalysts. Under similar conditions, alkylcyclohexanes (RC6) SRO is very slow and requires the addition of a controlled isomerization, i.e. a non-branching ring contraction. Non-branching ring contraction can be achieved using mesoporous crystalline materials, such as high Si/AI ratio faujasitic zeolites. We found that high activity hydrogenolysis catalysts, such as Ir, coupled with a mesoporous high Si/AI faujasite such as ECR-32 outperform conventional bifunctional catalysts for the selective conversion of naphthenes to acyclic paraffins.
26-0-05 - Reforming of FCC heavy gasoline and LCO with novel borosilicate zeolite catalysts C.Y. Chen and S.I. Zones
Chevron Research and Technology Co., Richmond, CA, USA, [email protected] In this paper we report the application of novel borosilicate zeolites in reforming of FCC heavy gasoline and light cycle oil (LCO). In this new technology, the borosilicate zeolite catalysts show breakthroughs in activity, selectivity, sulfur-tolerance and stability in terms of reforming these feedstocks which are unusually heavy and contaminated for conventional reforming processes. This new technology demonstrates the value of combining advanced catalytic materials with novel engineering processes to meet the demand for making advances in product-generating technologies.
160 21 - Nanocomposite Fundamentals and Applications (Wednesday am)
21-K-01 - Zeolite-based nanocomposites: synthesis, characterization and catalytic applications B.V. Romanovsky
Chemistry Department, Moscow State University, [email protected], Russia The oxidative in-situ degradation of mono and polynuclear complexes of transition metals within the Y zeolite supercages has been employed to produce an array of oxide nanoclusters encapsulated in the intercrystalline voids of the matrix. The resulting materials were characterized by using a number of experimental techniques. The nanocomposites synthesized by such a way display extraordinary high activities in the model reactions of CO and MeOH oxidation.
2 1 - O - 0 2 - Methods of synthesis for the encapsulation of dye molecules in
molecular sieves M. Wark (a), M. Ganschow (a), Y. Rohlfing (b), G. Schulz-Ekloff (a) and D. W6hrle (b)
a Institute of Applied and Physical Chemistry, University of Bremen, Germany, mwark@chemie, uni-bremen,de b Institute of Organic and Macromolecular Chemistry, University of Bremen, Germany Several methods for the stable encapsulation of various dyes in different molecular sieve hosts were successfully developed. The dye molecules are monomerically included in the void structure of the molecular sieves. The high variability in the anchoring method togethe r with the possibility to tune the morphologies of the molecular sieves will be of importance regarding the potential applications of these composites in optical micrometer-sized devices.
2 1 - O - 0 3 - M C M - 4 1 silica monoliths and diluted magnetic semiconductors" a
promising union for fabricating nanosized quantum wires F. Brieler(a), M. Brehm (a), L. Chen (c), P.J. Klar(c)*, W. Heimbrodt(c) and M. Fr6ba(a,b)* (a) Institute of Inorganic and Applied Chemistry, University of Hamburg, Hamburg, Germany (b) Institute of Inorganic Chemistry, University of Erlangen-Nuremberg, Erlangen, Germany Fr~176 (c) Department of Physics and Materials Science
Centre, Philipps University of Marburg, Marburg, Germany Here we report on the first synthesis and characterization of nanostructured Cd~.• • within the mesoporous system of MCM-41 silica. Several characterization techniques (e.g. TEM, XRD, nitrogen physisorption, x-ray absorption and PLE spectroscopy have been applied to show the preservation of the pore structure as well as to investigate the structure and physical properties of the included diluted magnetic semiconducting guest species. The obtained results reveal a coating of the inner surface of the mesoporous silica matrix by CdS which is almost statistically doped with magnetic localised Mn 2§ ions.
161
2 1 - O - 0 4 - Potential microlasers based on AIPO4-5/DCM composites O. WeiBa, F. Schtith a, L. Benmohammadi b and F. Laeri b
aMax-Planck-Institut fi2r Kohlenforschung, 45470 Miilheim, schueth@mpi-muelheim, mpg.de, Germany, bDarmstadt University of Technology, 64289 Darmstadt,, Germany Via in situ inclusion perfect hexagonal grown A1PO4-5 crystals were loaded with the laser dye DCM. The highest dye concentration is located in the middle of the crystals decreasing to the ends, showing that the dye is icluded in the early times of crystals growth. As DCM exceeds the pore diameter of A1PO4-5 (7,3 A) mesopores are induced during incorporation. Spectroscopic investigations proved the alignment of the dye molecules within the onedimensional channel system of the AFI structure. Data from literature show that DCM undergoes trans-cis photoisomerization. As spectra of DCM in A1PO4-5 indicate the presence of another absorbing species it is suggsted that a mixture of trans and cis DCM is present in the pores.
21-O-05 - Light-emitting BN, Si, and SiC nanoparticles encapsulated in molecular sieves Xiaotian Li (a), C. Shao (a), F. Gao (a), S. Qiu (a*), F.-S. Xiao (a) and O. Terasaki (b)
a Department of Chemistry and Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, [email protected], China b Department of Physics, Graduate School of Science, Tohoku University, Sendai 980-77, Japan Nanoparticles of Si, BN, and SiC encapsulated in zeolites, such as ZSM-5, L, APO-5, and MCM-41, have been successfully prepared and strong visible photoluminescence (PL) have been observed at room temperature. Analysis of the PL spectra leads us to proposing that the transformation from indirect-gap semiconductor materials to quasi-direct-gap ones by encapsulation in the channels of zeolites is the possible origins of the strong PL. 2 0 - Zeolite Membranes and Films (Wednesday am)
20-O-01 - Polyamines as strong covalent linkers for the assembly of mono and double layers of zeolite crystals on glass K. Ha, Y.S. Chun, A. Kulak, Y.S. Park, Y.-J. Lee, and K.B. Yoon*
Center for Microcrystal Assembly, Department of Chemistry, Sogang University, Seoul 121742, KOREA Introduction of polyamines led to a remarkable increase in the strength of the binding between the zeolite crystals and glass compared to those made by direct covalent linkages between the surface-bound AP, EP, CP, and hydroxyl groups. Such a result is proposed to arise from the ability of the large polyamine linkers to position in such a way between the two uneven surfaces, that results in the large increase in the number of covalent linkage between the multiple amine groups and the surface-bound EP or CP groups. Such a remarkable increase in the binding between zeolite crystals and glass substrates allowed us successful assembly of double layers of zeolite crystals.
162
2 0 - 0 - 0 2 - The use of seeds in the synthesis of mono-and bi-layered zeolite membranes L. Gora a, G. Clet b, J.C. Jansen a and Th. Maschmeyer a*
aLaboratory for Applied Organic Chemistry and Catalysis, DelfiChemTech, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands bLaboratoire de Catalyse et Spectrochimie, ISMRa, University of Caen 6, Bd du Mardchal Juin 14032 Caen (cedex)- France *tel..'+31 15 278 8826, fax.:+31 15 278 4289, e-mail: [email protected] Supported zeolite Y, silicalite-1, A and a composite of silicalite-1 on A can be synthesised in a membrane configuration in a reproducible manner. Synthesis techniques using seeds were applied in the membrane preparation. The double layer type membrane has great potential in the bifunctional operation in one integrated unit.
2 0 - 0 - 0 3 - Growth of oriented mordenite membranes on porous ct-AI203 supports G. Li, X. Lin, E. Kikuchi and M. Matsukata*
Department of Applied Chemistry, Waseda University, [email protected], Tokyo, Japan. A highly oriented mordenite membrane with c-axis of crystals perpendicular to the support surface was successfully prepared on a porous c~-alumina support. Seeding was essential to form a compact layer of mordenite. Based on the XRD and SEM results, it was concluded that "evolutionary selection" mechanism significantly contributes to the formation of a sharply oriented mordenite layer. Pervaporation results for separation of a water/iso-propanol (10:90, w/w) mixture showed highly preferential permeation (a=3615) of water through the oriented mordenite membrane.
2 0 - 0 - 0 4 - Depth-sensitive structural study of silicalite-1 films with grazing incidence X-ray diffraction S. Mintova(a), T.H. Metzger(b) and T. Bein(a)
aDepartment of Chemistry, University of Munich, Butenandtstr. 11, 81377 Munich, Germany, svetlana, mintova@cup, uni-muenchen, de bEuropean Synchrotron Radiation Facility, ESRF, BP 220, Grenoble, France, metzger@esrffr The change of crystal orientation within different MFI zeolite film structures was followed with the depth-sensitive grazing incidence diffraction technique. The measurements of the adsorbed and grown zeolite films at different incident and exit angles reflect the distribution of the crystal orientation along the film thickness. With increasing zeolite film thickness most of the crystals change their b-axes orientation from parallel to perpendicular to the sample's surface.
163
20-0-05Regeneration of supercritical carbon dioxide supported MFI zeolite and mesoporous silica membranes
by alumina
K.J. Chao *l, C.H. Kao I, Y.W. Chiu 2, X.R. Lin 2 and C.S. Tan .2
Departments of Chemistry I and Chemical Engineering 2, National Tsinghua University, Hsinchu 300, Taiwan e-mail." kjchao@mx, nthu. edu. tw The regeneration of supercritical carbon dioxide from a mixture containing caffeine by microporous MFI zeolite and mesoporous silica membranes supported on alumina was studied. The experimental data show that a caffeine rejection higher than 90% or 70% and a permeation flux of supercritical carbon dioxide more than 0.05 or 0.07 mol/mZ/s could be obtained at 10.5 MPa.
0 9 - Crystal Structure Determination (Wednesday am) 09-O-01 - Localisation of K + ions in (Na,K)-LSX and K-LSX zeolites by Rietveld analysis and 39K N M R spectroscopy. A new cationic site in the orthorhombic dehydrated K-LSX at room temperature J.L. Paillaud (a), P. Caullet (a), L. Delmotte (a), J.C. Mougenel (a), S. Kayiran (a) and B. Lledos (b)
a Ecole Nationale Sup~rieure de Chimie de Mulhouse, [email protected], France; b Air Liquide, Jouy-en-Josas, France A LSX zeolite sample was studied under its as-made form and its fully exchanged potassium form. Upon dehydration, a lowering of the symmetry is observable at room temperature. This phenomenon was confirmed by MAS NMR spectroscopy. The structure reveals for the first time a simultaneous occupancy of sites I and I' by potassium cations. This is due to a shift of site I from the centre of the D6R unit. 39Kwide line NMR spectroscopy confirms the Rietveld analysis, especially the absence of K + ions on site I in the as-made Na72,Kz4-LSXsample.
0 9 - 0 - 0 2 - N M R crystallography of AIPO4-CJ2 F. Taulelle and C. Huguenard
RMN et Chimie du Solide, UMR 7510 ULP-Bruker-CNRS, Universit6 Louis Pasteur, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France. e-mail. [email protected] AIPO4-CJ2 is an aluminophosphate with an open framework structure. This compound has been studied by in-situ NMR to follow its crystallogenesis. It has also been characterized recently by different types of high resolution solid state NMR methods. F-P and F-A1 MAS HETCOR have been used to prove the disordered nature of units building the solid, those with a fluorine in bridging position and those with hydroxide at the same bridging positions. A1PO4-CJ2 is considered here to illustrate its crystallographic structure determination by solid state NMR of the powder. The main steps of NMR crystallography are described in this contribution: topological analysis, space group and metric determination.
164 0 9 - 0 - 0 3 - FOS-5, a novel zeotype with 3D interconnected 12- ring channels T. Conradsson, Xiaodong Zou and M.S. Dadachov
Structural Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden An organically templated microporous germanium dioxide, FOS-5, with a novel zeotype
topology, [Ge32064]has been synthesised under hydrothermal conditions and characterised by single-crystal X-ray diffraction and thermogravimetric analysis. The compound crystallizes in the centred tetragonal space group I41/amd with a - 26.017(3), c = 27.218(3) A, V = 18421(4) A 3 and Z=8. The structure is stable up to 723K, sufficiently high for the complete removal of the organic guest molecules. Single-crystal diffraction data have been collected and the crystal structures were successfully solved and refined for both the as-synthesised and the detemplated forms. The compound has a three-dimensional framework structure, built up by GeO4 vertex connected tetrahedra to form intersecting 12-membered ring channels along all the three crystallographic axes. The free diameters of the channel apertures are 5.8 by 6.0 A along both the [100] and the [010] directions and 6.4 A along the [001] direction. Fluorine ions inserted in the [Ge8Ol6] double 4-rings are charge compensated by protonated trimethylamine cations encapsulated in the large channels.
09-0-04Neutron diffraction exchanged X and LSX zeolites
study
of protons
in four
lanthanum
D.H. Olson a, B.H. Toby b and B.A. Reisner b
a) University of Pennsylvania, Philadelphia, dholson@seas,upenn, edu," b) NIST, Gaithersburg, USA The positions of protons and other extra-framework species in HLaLSX dehydrated at 200 and 400~ HLaNaLSX dehydrated at 515~ and LaX dehydrated at 200~ have been determined by neutron powder diffraction. Four hydrogen sites have been found, three framework and one nonframework a La-hydroxyl proton. The results are compared to IR spectroscopic assignments. Protons have been located in the supercage bonded to the O1 and 02 oxygen atoms. For one material, HLaLSX dehydrated at 400~ protons were also found bonded to 03 oxygen atoms.
0 9 - 0 - 0 5 - Optimized synthesis and structural properties of lithosilicate RUB-29 S.H. Park ~ J.B. Parise ~ and H. Gies #
~ of Geosciences, +Chemistry Dpt, State University of New York at Stony Brook, USA, # Institutf~r Geologie, Mineralogie, Geophysik, Ruhr-Universitdt-Bochum, Germany The structure of a new member of the lithosilicate family, RUB-29 (Cs14Li24[LilsSi72Olv2]e 14H20), was determined using NMR spectroscopy, synchrotron single crystal and neutron powder diffraction (NPD). The material contains Si- and Li-centered tetrahedra segregated into alternating layer-like building units, producing a framework containing a three dimensional system of channels bounded by 8- and 10-membered rings. Lithium cations play an important role in the framework and in pore systems, and are responsible for structurally and physico-chemically unique properties of the material.
165
2 7 - Selective Oxidation and Sulfur Resistance (Thursday pm) 27-O-01 - Singular catalytic properties of Ti-MWW in the selective oxidation of alkenes P. Wu a, T. Komatsub, T. Yashimab and T. Tatsumi a ~Division of Materials Science & Chemical Engineering, Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama240-8501, Japan bDepartment of Chemistry, Tokyo Institute of Technology, 2-12-10okayama, Meguro-ku, Tokyo 152-8551, Japan Ti-MWW has been hydrothermally synthesized in the presence of boric acid and with piperidine as a structure-directing agent. Acid treatment of the as-synthesized samples is necessary for removing the extrafi'amework Ti species. Ti-MWW nearly flee of anatase species with Si/Ti ratio as low as 40 is prepared. Ti-MWW effectively catalyzes the oxidation of linear alkenes with H202, and also shows a significant activity for the sterically demanding reactions such as oxidation of cyclohexene with tert-butyl peroxide. Ti-MWW exhibits a singularity, never observed on the other titanosilicate, that it selectively epoxidize the trans isomer in the oxidation of geometric mixture of cis/trans alkenes.
2 7 - 0 - 0 2 - Epoxidation of propylene over TS-1 containing trace a l u m i n u m Xinwen Guo, Xiangsheng Wang, Min Liu, Gang Li, Yongying Chen and Jinghai Xiu
State Key Laboratory,Dalian University of Technology, [email protected], Dalian, China Titanium silicalite (TS-1) containing trace aluminum was successfully synthesized using TPABr as the template and silicon sol as silicon source in a 100L stainless steel autoclave. The synthesized TS-1 exhibits high activity and low selectivity for propylene oxide (PO) in the epoxidation of propylene with dilute H202. The selectivity of PO can reach about 90 % through adjusting the pH value of the reaction mixture. But, extra amount of basic substance will make the utilization and the conversion of H202 decrease. The utilization of H202 increases after acid treatment for the low Si/Ti ratio TS-1, but the utilization of HzO2does not change for the high Si/Ti ratio TS-1 in the epoxidation of propylene. Experimental results of thermal-stability show that the as-synthesized TS-1 calcined between 540~ and 900~ exhibits high activity and thermal stability.
2 7 - 0 - 0 3 - One step benzene oxidation to phenol using N20 over acid zeolites G. Juttu and R.F. Lobo
Department of Chemical Engineering, University of Delaware, [email protected], Newark DE, USA We have investigated the gas phase partial oxidation of benzene to phenol over zeolite HMCM-22 using as the oxidant. H-MCM-22 is active (15% benzene conversion at 603 K) and nearly 100% selective for the partial oxidation of benzene to phenol. We have also investigated the reaction in an in-situ IR cell. Both benzene and phenol interact strongly with the Bronsted acid site whereas does not interact strongly with the zeolite. We find the presence of Bronsted acidity is critical for the reaction and we found no correlation of the activity with the iron content, as reported previously by others.
166
2 7 - 0 - 0 4 - Dual pathways for benzene hydrogenation on Pt/mordenites: implication for sulfur tolerance L. Simon a'b, J.G. van Ommen b, A. Jentys a and J.A. Lercher a
a Technische Universitgit Miinchen, Garching, [email protected], Germany bFaculty of Chemical Technology, University ofTwente, Enschede, The Netherlands The catalytic testing of Pt supported MOR with various Na+/H + ratio shows that benzene hydrogenation occurs via two pathways (i) on metal sites and (ii) on Bronsted acid sites with hydrogen spilt over from the close metal surface. In the presence of sulfur the metal surface is poisoned and the catalytic activity remains on Bronsted acid sites. Due to a subtle balance between a high Bronsted acid site concentration that deactivates the catalysts by coking and metal sulfur poisoning and a low Bronsted acid site concentration, i.e., a low benzene conversion on the acid sites, Pt supported on partially exchanged MOR showed a higher rate of benzene conversion and a higher sulfur resistance than on all other catalysts.
27-0-05 - Sulfur resistance of PtPd catalysts: preparation, characterization and catalytic testing K. Thomas, C. Binet, T. Chevreau, D. Cornet and J.-P. Gilson
Laboratoire de Catalyse et Spectrochimie, ISMRA, Caen, France ([email protected]) Pt, Pd and PtPd metallic precursors are deposited on amorphous silica aluminas and dealuminated FAU zeolites. The catalytic activity is measured in the hydrogenation of toluene in the absence or presence of sulfur (200 ppm). In the absence of sulfur, alloying Pt with Pd decreases the hydrogenation activity. In general, catalysts made from ammoniated precursors are the most active with one remarkable exception. In the presence of sulfur, thioresistance is a function of reaction temperature, i.e. sulfur coverage of the metallic phase. Pd increases substantially the sulfur resistance. The effect of support acidity on thioresistance is observed only at high sulfur coverage. 03 - New Methods of Zeolite Synthesis (Thursday pro)
03-K-01 - Application of combinatorial tools to the discovery commercialization of microporous solids: facts and fiction
and
J. Holm~ren a, D. Bern a, M. Bricker a, R. Gillespie a, G. Lewis a, D. Akporiaye b, I. Dahl b, A. Karlsson ~ M. Plassen b and R.Wendelbo b
UOP LLC, [email protected], Des Plaines, IL, USA; b SINTEF, Norway During the past three years, combinatorial tools and methods have received increasing amounts of attention as potentially enabling methodologies for the chemical industry. We have developed an integrated End-to-End TM combinatorial catalyst discovery system, which allows us to perform all the critical catalyst processing operations combinatorially. A critical component of this system is a combinatorial multiautoclave assembly, which can be used to explore hydrothermal space efficiently and effectively. Our recent results illustrate the applicability of this capability to both the discovery and scale-up of microporous solids. The expected impact of these combinatorial tools in new product commercialization and the chemical industry will be discussed.
167
03-0-02 - Mesoporous zeolites C.J.H. Jacobsen, J. Hou~vicka, A. Carlsson and I. Schmidt* Haldor Topsoe A/S, Nymollevej 55, DK-2800 Lyngby, Denmark Mesoporous zeolite crystals have already been shown to exhibit promising properties in catalytic processes, here, it is shown how mesoporous ZSM-5 crystals can be synthesized by a variation of the Confined Space Synthesis method. It is discussed how the synthesis conditions influence the morphology of the zeolites.High nucleation rates favour formation of nanosized zeolites whereas low nucleation rates favour formation of mesoporous zeolites. In this way, it is possible to obtain either large (1-10 ~tm) or small (100-500 nm) mesoporous zeolite crystals. The structure and morphology of the mesoporous zeolite crystals are illustrated by transmission and scanning electron microscopy. Mesoporous zeolites have high mesopore volumes (0.8-1.2 ml/g) and high mesopore surface areas (100-200 mZ/g). The advantages of mesoporous zeolite crystals as heterogeneous catalysts are discussed.
03-0-03 - Synthesis of novel zeolites SSZ-53 and SSZ-55 using organic templating agents derived from nitriles S.A. Elomari and S.I. Zones Chevron Research & Tech. Co., [email protected], Richmond 94802 CA, USA In our quest for finding novel high silica zeolites using amine-based structure-directing agents (SDA) in our synthetic schemes, here we report a new class of SDA derived from carbonitriles. This class of SDA was designed in an attempt to overcome making cage-like zeolitic products commonly produced by using polycyclic rigid SDA or making other known zeolites such as MFI and MTW usually produced by using freely rotating SDA. The use of this class of SDA in zeolite synthesis did not only avoid making such materials, but has led, among others, to new high silica large pore zeolites SSZ-53 and SSZ-55. In our presentation we will describe these new SDA and their zeolitic products.
03-0-04 - Synthesis of IFR-type zeolites optimized for spectroscopic study B.S. Duersch and L.W. Beck*
The University of Michigan, Department of Chemistry 930 N. University Ave., Ann Arbor, MI 48109-105.5 USA, * [email protected] The synthesis of highly ordered boron and aluminum containing materials of structure-type IFR is presented. The IFR-type zeolite materials synthesized by this method have exceptionally uniform particle size and crystal morphology. These materials exhibit improved resolution by NMR characterization including the partial resolution of crystallographic T-sites in these acidic frameworks. The preferred synthesis conditions are more concentrated than previously reported and require much less SDA (ammonium cation). This synthesis procedure is both flexible and reliable yielding large uniform single crystals. The high-resolution of the NMR spectra indicate an unusual degree of short-range crystalline order for these materials.
168
03-0-05 - Competitive role of sodium and potassium cations during hydrothermal zeolite crystallization from Na20-K20-AI203-SiO2-H20 gels A.F. Ojo (a), F.R. Fitch (a), M. Btilow (a) and M.-L. Lau (b) a BOC Gases Technology, [email protected], Fax No. 908-771-6488, USA.
b Schering-Plough Research Institute, USA Zeolites A, F, Q, X and sodalite were synthesized hydrothermally from NazO-K20-A1203-SiOzH20 gels. The crystallization processes were monitored as a function of the fraction of sodium cations in the sodium-potassium cation gel system. Pure phases were obtained in three distinct alkali composition ranges: zeolite A was.crystallized at Na20/(Na20+K20) - 0.9 to 1.0, zeolite X at NazO/(NazO+K20) - 0.7 to 0.8, and zeolite F at NazO/(NazO+K20) < 0.5. The structuredirecting roles of these alkali cations, the phase evolution of products, as well as size and morphology of the crystals are discussed.
2 2 - Advanced Materials (Thursday pro) 22-O-01 - The effect of the location of framework negative charge on the ordering of templates in zeolite IFR R.E. Morris and L.A. Villaescusa
School of Chemistry, University of St. Andrews, Purdie Building, St. Andrews, Scotland KY16 9ST; reml @st-and.ac.uk The non-centrosymmetric ordering of benzylquinuclidinium structure directing agents inside the centrosymmetric IFR framework has been shown by single crystal X-ray diffraction and second harmonic generation measurements. The reasons behind this effect and the requirements of the zeolite structural architecture needed to show this ordering are discussed.
22-0-02 - A new family of microporous vanadium phosphates and related compounds with organic coordination Shouhua Feng*, Zhan Shi, Lirong Zhang, Hui Zhao, Dong Zhang and Zhiming Dai
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People's Republic of China, [email protected] A new family of microporous vanadium phosphates and related compounds with organic coordination were hydrothermally crystallized and their crystal structures were characterized by single crystal X-ray diffraction. Structural diversity of these open inorganic-organic hybrid materials derives from considerable variables for both inorganic and organic parts from the point of view of syntheses and structures. Current study in this field showed great challenges not only in crystal chemistry of microporous materials but also in biological properties such as helical array and ligand exchange.
169
2 2 - 0 - 0 3 - Catalytic properties of novel nickel(ll) phosphate with nanoporous structure J.-S. Chang, D.S. Kim, S.-E. Park, P.M. Forster, A.K. Cheetham b and G. Fereyc
aCatalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology, Taejon, Korea," bMaterials Research Laboratory, University of California, Santa Barbara, USA," Clnstitut Lavoisier, UMR CNRS 173, Universitd de Versailles Saint Quentin, Versailles, France Ni (II) phosphate, VSB-1, develops a unidimensional pore system which is delineated by 24 NiO6 and PO4 polyedra and the free diameter of the channel is estimated to be 8.8 A. It becomes microporous on calcination in air at 350~ For cyclodimerization of 1,3-butadiene, VSB-1 itself shows excellent selectivity for ethylbenzene. Reduced Ni-VSB-1 yields good selectivity for hydrogenation of 1,3-butadiene to butenes and Pd-containing VSB-1 exhibit good catalyst performance for direct production of H202 from H2 and O2.
2 2 - 0 - 0 4 - Characterization of corrosion-resistant zeolite coatings on A! alloys Huanting Wang, Zhengbao Wang, Xiaoliang Cheng, Anupam Mitra, Limin Huang, and Yushan Yan
Department of Chemical and Environmental Engineering, University of California, Riverside, CA 92521, USA, yushan, [email protected]. Zeolite films have been developed for corrosion-resistant coatings on Al-alloys and other metals. In present work, thermal and thermal shock stability, and mechanical properties (cutting, impact, bending and abrasion) of ZSM-5 coatings on A1 alloys were investigated. The results show that the coatings have good thermal/thermal-shock stability, adhesion and wear-resistance, and are flexible to some extent. Therefore, zeolite coating is a potential candidate for corrosion protection of A1 alloys and other metals.
2 2 - 0 - 0 5 - Template synthesis and catalysis of bimetallic platinum-rhodium a n d - p a l l a d i u m nanowires in mesoporous materials A. Fukuoka (a), Y. Sakamoto (a), S. Inagaki (b), N. Sugimoto (b), Y. Fukushima (b), and M. Ichikawa (a)
a Hokkaido University, [email protected], Sapporo, Japan; b Toyota Central R&D Labs., Inc., Aichi, Japan Template synthesis of transition metal nanowires in mesoporous materials is presented. Pt, Rh, Pt-Rh, and Pt-Pd nanowires are synthesized in HMM-1 and FSM-16 by the photoreduction method. The bimetallic nanowires in HMM-1 are alloy crystallite with a necklace-like structure. The Pt-Pd wire/HMM-1 shows higher magnetic susceptibility at low temperature than the Pt wire. In butane hydrogenolysis, Pt-Rh wire/FSM-16 shows high selectivity to isobutane.
170 32 - Zeolite m i n e r a l s and H e a l t h Sciences (Thursday pm)
3 2 - O - 0 1 - B i o m e d i c a l a p p l i c a t i o n s of zeolites *K. Pavelic 1, B. Subotic I and M. Colic 2 IRudjer Boskovic Institute, Zagreb, Croatia," 2Molecutec Corporation., Goleta, USA pavelic@rudjer, irb. hr Natural and synthetic zeolites as well as other mesoporous and microporous solids are used in many industrial and household applications. However, it is less known that in recent years these exciting materials are increasingly being used in biomedical applications. In this review different current and possible future biomedical applications, together with our own research results obtained from studies of such materials, are critically described. Current needs for synthesis and characterization of novel mesoporous and microporous materials which would be better suited for biomedical applications are also described.
3 2 - 0 - 0 2 - Zeolites and other p o r o u s materials in the toxicity o f inhaled m i n e r a l dusts I. Fenoglio, L. Prandi, M. Tomatis and B. Fubini* Dipartimento di Chimica IFM, Universitb di Torino, Torino, [email protected] Some porous materials, typically fibrous erionite, are toxic per se. Others may be used as "model solids" to mimic real pathogenic minerals. It has been hypothesized that erionite catalyses free radical generation which damage DNA. Erionite released OH" only when incubated with ferric iron. Iron mobility in asbestos has been studied by means of cyclic voltammetry. Ferrosilicalite and one Fe-Y zeolite were "model solids" for iron mobility. Porosils have been employed in the study of silica cytotoxicity. Cell growth inhibition correlates with the outer surface, measured from particle morphology, but not with the BET surface, suggesting particle-cell contact as a primary step in cell growth inhibition. MCM-41 with spin active labels, in contact with cells, acted as a sensor of phagocytosis, the active nitroxide being quenched by cell generated oxidant.
3 2 - 0 - 0 3 - S t u d y of the reaction of a Ca-clinoptilolite and h u m a n bile R. Sim6n Carballo (a), G. Rodriguez-Fuentes (b), C. Urbina (c) and A. Fleitas (a) a Instituto Nacional de Angiologia y Cirugia Vascular, [email protected], Cuba b Instituto de Materiales y Reactivos, Univ. La Habana, [email protected], Cuba c Universidad Central de, [email protected], re, Venezuela The calcium exchanged form of the purified natural clinoptilolite (NZ) from the Tasajeras deposit, Cuba, is the active ingredient of a drug designed to reduce total blood cholesterol and prevent atherosclerosis. The study of the Ca2+-NZ - human bile reaction has revealed that it occurs through the adsorption of three major human bile compounds: bile acids, phospholipids and bilirubin. The adsorption of phospholipids on the external surface of the clinoptilolite crystals produces a phospholipids-zeolite interface with anionic activity that allows the adsorption of bile acids.
171
3 2 - 0 - 0 4 - In vitro adsorption of zearalenone by oetadecyldimethylbenzyl ammonium-exchanged clinoptilolite-heulandite tuff and bentonite A. Dakovic(a), M. Tomasevic-Canovic(a),V. Dondur(b), D. Stojsic(c) and G. Rottinghaus (d)
a ITNMS, [email protected], Belgrade, Yugoslavia," b Faculty of Physical Chemistry, Belgrade, Yugoslavia; c VMA Institute for Hygiene, Belgrade, Yugoslavia; d College Veterinary Medicine, University of Missouri, Columbia, USA Chemical modification of zeolitic tuff and bentonite with octadecyldimethylbenzyl ammonim ion (ODMBA) increased adsorption of zearalenone (ZEN) as the levels of ODMBA increased. The organozeolite required 10X less ODMBA than the organobentonite for maximum ZEN adsorption (100%). In addition, changing the pH from 3 to 9 had little effect on adsorption of ZEN on organozeolites.
3 2 - 0 - 0 5 - Zeolites in sexual confusion" slow release of pheromones J. Mufioz-Pallares, E. Primo, J. Primo and A. Corma
Instituto de Tecnolog[a Quimica (C.S.I. C-UP. V), Valencia. Spain Semiochemicals can be adsorbed in zeolites and their diffusion-desorption rate can be controlled by modifying the physicochemical and structural parameters of zeolites. By matching the nature of the semiochemical, its functional groups, and the framework, extraframework composition and pore topology of the zeolite, it is possible to design dispensers that allow to achieve the adequate air concentration of the pheromone (the most important group of semiochemical) within times long enough to be used for insect sexual confusion for the preservation of crops.
3 0 - Environmental Catalysis (Friday am) 30-K-01 - The local structures of transition metal oxides incorporated in zeolites and their unique photocatalytic properties M. Anpo* and S. Higashimoto
Dept. Appl. Chem., Osaka Prefecture University, [email protected], Japan Various microporous and mesoporous zeolite catalysts incorporated or encapsulated with transition metal cations such as M o 6§ V 5+, or Ti 4+ into their frameworks or cavities were synthesized by a hydrothermal synthesis method. In-situ spectroscopic techniques and analyses of the photocatalytic reaction products have revealed that these transition metal cations constitute highly dispersed tetrahedrally coordinated oxide species which enable the zeolites to act as efficient and effective photocatalysts for the various reactions such as the decomposition of NOx into N2 and 02 and the reduction of CO2 with H20 into CH3OH and CH4. The charge transfer excited triplet state of these oxides, i.e., (Mo 5+- O')*, (V 4+ - O')*, and (Ti 3§ O')*, was found to play a significant role in the unique and efficient photocatalytic reactions on various zeolitic materials incorporated with Mo, V, or Ti oxide species.
172
3 0 - 0 - 0 2 - Characterization and performance of ex-framework FeZSM-5 in catalytic N 2 0 decomposition J. P6rez-Ramirez a'*, G. Mul a, F. Kapteijn a, I.W.C.E. Arends b, A. Ribera b and J.A. Moulijn a
a Industrial Catalysis, b Laboratory for Organic Chemistry and Catalysis, Delft University of Technology, [email protected], The Netherlands Catalytic N20 decomposition was investigated over FeZSM-5 prepared by a novel exframework method. This method comprises the introduction of Fe in the MFI framework, followed by calcination and steam treatment to extract the iron to extra-framework positions. The ex-framework method induces superior activity for direct N20 decomposition, compared to FeZSM-5 catalysts prepared by solid and aqueous ion-exchange methods. The extraordinary catalytic performance of ex-FeZSM-5 is attributed to the highly dispersed state of the Fe in the zeolite matrix and the Fe(III)/Fe(II) redox behaviour of a significant fraction of the iron centers in the catalyst.
3 0 - 0 - 0 3 - Effect of carbon number in hydrocarbon reductant on the selective catalytic reduction of NO over cation-exchanged MFI zeolites A. Shichi, Y. Kawamura, A. Satsuma and T. Hattori
Applied Chemistry, Nagoya University, [email protected], Nagoya, Japan In order to examine the possibility of using higher hydrocarbon as a reductant for the selective catalytic reduction of NO, the effect of carbon number in n-alkane was investigated over Cu-, Ag- and Co-MFI zeolites. On all the catalysts, NO conversion showed a volcano-type correlation to the carbon number in n-alkane, although the carbon number at maximum NO conversion varied with the exchanged cation species and the presence of water vapor. The NO conversion increased with increasing carbon number, while the deactivation by carbonaceous deposition and/or strongly adsorbed species became significant. The catalyst deactivation could be suppressed by the presence of water vapor and by periodic SCR reaction operation.
3 0 - 0 - 0 4 - The temperature-dependent storage of NOx on metal-containing zeolites under dry and wet conditions R. Fricke, M. Richter, E. Schreier, R. Eckelt and H. Kosslick
Institute of Applied Chemistry (ACA), Berlin, [email protected] The development of new catalysts for the storage and reduction of NOx from lean-burn engines is a challenge to meet the demands of the Euro IV norm in 2005. The new catalyst systems should also be able to adsorb NO• already at comparable low temperature and desorb it at high temperature. Cu and Ba exchanged zeolites of various types (Y, MOR, MFI, L, CHA) and their ability to adsorb NOx isothermally from a dry feed and to desorb it under temperature-programmed conditions (55-600~ are described. Their NOx adsorption /desorption properties under wet conditions are compared. Furthermore, a zeolite material modified by manganese oxide is developed which is able to adsorb NOx from a wet feed already at temperatures as low as 120 ~ and desorb it above 350~
173
3 0 - 0 - 0 5 - Catalytic destruction of chlorinated VOCs. Influence of characteristics of Pt/HFAU catalysts on the destruction of dichloromethane L. Pinard, J. Tsou, P. Magnoux and M. Guisnet
Laboratoire de Catalyse en Chimie Organique, UMR CNRS 6503, patrick.magnoux@univpoitiers fr, France Catalytic oxidation of dichloromethane (1000 ppm, 4% steam) was investigated over a series of Pt/HFAU catalysts differing by their Pt content (from 0 to 1.0wt%) and their framework Si/A1 ratio (5, 17, 47 and 100). The higher the reaction temperature, the faster the CH2C12 oxidation. For a given zeolite support, the rate of CH2C12 transformation is independent of the platinum content. On the other hand, the CH2C12 oxidation into CO2 appears as a bifunctional mechanism: the oxidation rate increases firstly with the Pt content (or nPt) then remains constant above a certain value of nPt. The support plays also an active role for this oxidation: the higher the zeolite acidity, the faster the CH2C12 oxidation. Furthermore, Lewis acid sites seem to intervene in a positive way for CH2C12 transformation.
2 8 - Confinement and Physical Chemistry for Catalysis (Friday am) 28-O-01 - Reactivity enhancement by molecular consequence of released single-file constraints
traffic
control-
a
P. Br~uer and J. K~irger
Universitcit Leipzig, Abteilung Grenzfldchenphysik, kaerger@physik, uni-leipzig, de, Germany
Linndstrasse 5, D-04103 Leipzig,
Reactivity enhancement by molecular traffic control has been postulated to occur as a consequence of the reduced mutual transport inhibition if reactant and product molecules are able to use different pathways. Representing the catalyst as a network of intersecting singlefile systems, the concept of molecular traffic control is investigated quantitatively. Differences in the accommodation probability of the reactant and product molecules in the individual single-file systems are in fact found to lead to the predicted output enhancement of product molecules. This gain in reactivity is correlated with the establishment of concentration gradients which counteract transport inhibition by single-file confinement.
2 8 - 0 - 0 2 - Aromatization of n-hexane over Z n N i / H Z S M - 5 catalyst induced by microwave irradiation J.Z. Gui (a), H.S. Ding (a), N.N. Liu (a), Y.R.Gao (a), Z.L. Cheng (a), X.T. Zhang (a), B. Ma (a), L. Song (a,b), Z.L. Sun (a,*) and L.V.C. Rees (b)
a Dept. of Appl. Chem., Fushun Petroleum Institute, Fushun, P . R . China, [email protected], b Dept. of Chem., The University of Edinburgh, Edinburgh, UK The aromatization of n-hexane over a ZnNi/HZSM-5 catalyst has been investigated using two different heating methods; microwave irradiation heating and conventional heating. The characteristics of the ZnNi/HZSM-5 catalysts prepared under the two heating methods respectively have also been studied using XRD, BET and TGA techniques. The influence of the microwave on the properties and the catalytic performance of the catalysts were given in details. The reaction mechanisms were also discussed.
174
2 8 - 0 - 0 3 Artificial photosynthesis using zeolites N. Castagnola and P.K. Dutta
Department of Chemistry, The Dutta. l @osu. edu
Ohio State University, Columbus, Ohio 43210,
The goal of this study is to assemble a chemical architecture that can split water into hydrogen and oxygen using sunlight. Zeolites provide opportunities for novel spatial arrangement of molecules. The photochemical process begins with electron transfer from sensitizers to acceptor molecules in the zeolite. We find that the short-circuiting back electron transfer process is significantly slower in the zeolite and the intrazeolitic packing of the acceptor molecules also leads to long-lived charge separation and the charge-separated species can be chemically exploited by suitable catalysts. The challenge is to incorporate all these elements of the system into a single architecture and we are examining zeolite membranes for this purpose.
2 8 - 0 - 0 4 - Synthesis of macrocycles using molecular sieve catalysts M. Radha Kishan, N. Srinivas, S.J. Kulkarni*, M. Ramakrishna Prasad, G. Kamalakar and K.V. Raghavan.
Catalysis Group, Indian Institute of Chemical technology, Hyderabad, India For the first time we report the synthesis of macrocycles like calixpyrrole, cyclotriveratrylene (CTV), cyclotetraveratrylene (CTTV), porphyrine etc over molecular sieve as a catalyst. Calixpyrroles are synthesized from pyrrole and a ketone like acetone over MCM-41 under reflux conditions using suitable solvent. In case of MCM-41 cyclic calixpyrroles were obtained. On the other hand due to shape selectivity in case of Y zeolite linear di-, tri- and tetra- polypyrroles were obtained and cyclic tetramers were not observed. The mechanism of the synthesis of calixpyrrole is either by the dimerization of dimer with simultaneous cyclization to cyclic tetramer or cyclization of linear tetramer via recoil phenomenon.
2 8 - 0 - 0 5 - Effect of single-file diffusion on the hydroisomerization of 2,2-dimethylbutane on platinum loaded H-mordenite F.J.M.M. de Gauw, J. van Grondelle and R.A. van Santen
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven University of Technology, Eindhoven, The Netherlands - F.J.M.M.de. [email protected] The effect of single-file diffusion limitation on the rate of an irreversible first order catalytic reaction was studied both theoretically and experimentally. A rate equation was derived using a relation between the effective diffusion constant and the concentration of adsorbed molecules under single-file conditions which is valid on the time scale of catalytic reactions. The hydroisomerization of 2,2-dimethylbutane on platinum loaded large crystallites of HMordenite was used as a test reaction to verify the theoretical results.
175
0 4 - Isomorphous Substitutions (Friday am) 0 4 - O - 0 1 - Direct synthesis of C u ( I ) - M F I zeolite in the presence o f C u ( I I )
methylamino complexes as mineralizing and reducing agents S. Valangea, b, F. Di Renzo c, E. Garroned, F. Geobaldo~, B. Onida d and Z. Gabelica a a ENSCMu, GSEC, 3 Rue A. Werner, F-68093, Mulhouse, France, b Present address 9 LACCO, UMR CNRS 6503, ESIP, 40 Av. du Recteur Pineau, F-86022 Poitiers, France, [email protected], ~ ENSCM, 8 rue de l'Ecole Normale, F-34053 Montpellier, France, a Politecnico di Torino, Corso Duca degli Abruzzi 24, 1-10129 Torino, Italy We report for the first time the direct synthesis of a Cu bearing MFI zeolite using amino complexes as mineralizing agents and give experimental evidence of an in-situ reduction of Cu(II) to Cu(I) by methylamine. Cu(I) ions alone never integrate the Al-free MFI framework, while they are partly incorporated in the A1-MFI crystals. Investigation of the nature of the Cu(I) ions in this particular (Cu,A1)-ZSM-5 by UV-vis and FTIR shows that the Cu(I) species are strongly anchored to the MFI framework and are particularly stable and resistant to elution. The kinetics of the Cu(I) incorporation is discussed on the basis of the particular structural model proposed for (Cu,A1)-ZSM-5 0 4 - 0 - 0 2 - Preparation and catalytic properties o f a n o v e l t y p e o f zeolites with basic properties S. Ernst, M. Hartmann and S. Sauerbeck Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany, sernst@rhrk, uni-kl, de Novel basic zeolite catalysts are obtained by ammonia treatment of crystalline, microporous aluminosilicates at temperatures from 700~ to 900~ The resulting materials are active catalysts in the Knoevenagel condensation of benzaldehyde with malononitrile, presumably due to the presence of nitrogen-containing species bound to the crystalline framework. As active sites of the new materials both, terminal -NH2 and bridging -NH-groups can principally be envisaged. A decrease in catalytic activity is observed upon extended exposure to moisture due to hydrolysis of the Si-NH2 groups. The initial catalytic activity, however, can easily be restored by a new ammonia treatment.
04-0-03 - Preparation and characterization of iron-substituted zeolites G. Giordano (a), A. Katovic(a), A. Fonseca (b) and J. B.Nagy (b) (a) Universitdt della Calabria, RENDE (CS), Italy (b) Laboratoire de RMN, FacultOs Universitaires Notre-Dame de la Paix, NAMUR, Belgium Iron is introduced into the framework of three different zeolite-types: MFI, MTW and TON by direct hydrothermal synthesis from alkaline reaction mixtures containing iron complexes (oxalate or phosphate). The synthesis conditions for each zeolite-type and the results on the characterization of the samples by XRD, AAS, thermal analysis, SEM and 29Si-, 13C- and 3~p_ NMR spectroscopy are discussed.
176
0 4 - 0 - 0 4 - Influence of the nature of T atoms on the m o r p h o l o g y and crystal size of KZ-2 and ZSM-22 zeolites isomorphously substituted with Al or Fe M. Derewifiski*, M. Kasture a, J. Kry~ciak and M. Stachurska
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, 30-239 Cracow, Niezapominajek Str. 8, Poland, e-mail." ncderewi@cyf-kr, edu.pl on leave from National Chemical Laboratory, Pune, India Syntheses of KZ-2 and ZSM-22 zeolites isomorphously substituted with iron or aluminium were carried out for a wide range of the Si/T ratio (T=A1, Fe). Effect of the gel composition on size and morphology of the crystals formed was studied. It has been shown that using diethylamine as a template it is possible to synthesize iron containing KZ-2 zeolites with the similar crystals (in size and morphology) independently of Si/Fe ratio in gel. No such effect was observed when the syntheses were carried out in the presence of aluminium in the gel. The results point to an important role of the nature of T cations in the process of the zeolite crystal growth.
0 4 - 0 - 0 5 - Synthesis and characterisation of novel large-pore vanadosilicates A M - 1 3 and A M - 1 4 P. Brand~o a'b, A. Philippou a, N. Hanif% J. Rocha b and M. Anderson a
aDepartment of Chemistry, UMIST, PO Box 88, Manchester M60 1QD, UK bDepartment of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal, [email protected] The novel large-pore vanadosilicates AM-13 and AM-14 (Aveiro-Manchester, structure number 13 and 14) containing stoichiometric amounts of vanadium (Si/V - 10 and 4, respectively), have been synthesised. Characterisation techniques such as bulk chemical analysis (ICP), powder X-ray diffraction (XRD), scanning (SEM) and transmission (TEM) electron microscopy, and N2, n-hexane, benzene, tripropylamine and perfluorbutylamine adsorption measurements were used for the structural studies. The acid-base and redox properties of these materials were assessed by the conversion of isopropanol and ethanol oxidation, respectively. Both materials exhibit high selectivity to acetaldehyde indicating that these two novel vanadosilicates are promising redox catalysts. 1 4 - F r a m e w o r k s , Cations, Clusters (Friday am)
14-O-01 - Imaging the mesopores in zeolite Y using three-dimensional transmission electron microscopy A.H. Janssen (a), A.J. Koster (b) and K.P. de Jong (a)
a Department of Inorganic Chemistry and Catalysis, Utrecht, The Netherlands [email protected]; b Department of Molecular Cell Biology, Utrecht, The Netherlands A 3D-TEM study on a series of Y zeolites reveals the mesopores (generated by steaming and/or acid leaching) with great clarity. Both the diameters and shapes of the visualised pores correspond very well with nitrogen physisorption measurements of the entire sample. Also amorphous alumina in the mesopores and on the external surface can be visualised, which is in agreement with results obtained by XPS on these samples. From these results a more detailed model for the formation of mesopores in zeolite Y is proposed.
177
14-O-02
- 170
NMR studies of the structure and basic properties of zeolites
D. Freude, T. Loeser and U. Pingel
Universitgit Leipzig, Abteilung Grenzfli~chenphysik,[email protected] DOR and MQMAS NMR techniques were applied in the high field of 17.6 T to the study of several oxygen-17 enriched zeolites with the ratio Si/AI = 1. The tendency that the isotropic chemical shift of the 170 NMR decreases with increasing bond angle (or s-character of the oxygen hybrid orbital) was confirmed by this study. A quite linear correlation exists for the oxygen sites in the zeolites A and LSX, if the data are limited to the sodium form of the hydrated zeolites. Ion exchange of the hydrated zeolites (Li-, Na-, K-, Rb-, Cs- and T1 forms) generates strong chemical shift effects. The increase of the basicity of the oxygen framework of the zeolite LSX is reflected by a downfield shift of ca. 10 ppm going from the lithium to the cesium form. The substitution of sodium by thallium in the zeolite A causes a shift of 34 ppm for the 03 signal.
1 4 - O - 0 3 - Theoretical interpretation of UV-VIS spectra of Cu- and Agspecies in zeolites" structure v s . transition energies P. Nachtigall, M. Davidovfi, M. Silhan and D. Nachtigallovd
J. Heyrovskfi Institute of Physical Chemistry, Academy of Sciences of the Czech Republic and Center for Complex Molecular Systems and Biomolecules, DolejJkova 3, 182 23 Prague 8, Czech Republic The :,nteraction of Ag and Cu ions with MFI and ferrierite was studied with the combined quantam mechanics / interatomic potential function (QM-Pot) technique. The structure and coordination of Ag and Cu ions, Cu 2+ reduction, and photoluminescence spectra were investigated. The experimental data are analyzed in light of the results of the QM-pot compatational study. A consistent interpretation at the atomic scale level is offered and the implications for the catalytic activity of these systems are discussed.
14-O-04 - Silver ions and quantum-sized silver sulfide clusters in zeolite A D. Brahwiler, C. Leiggener and G. Calzaferri*
Department of Chemistry and Biochemistry, University of Bern, Switzerland *gion. calzaferri@iac, unibe, ch UV/vis
spectroscopic
studies
of
Ag+xNal2_xA, Ag+xCa2+_0.5xA and Ag~.5ZK-4
in
conjunction with molecular orbital calculations lead to the result that 4-ring coordinated Ag § is responsible for the deep yellow color observed in silver loaded zeolite A activated at room temperature. Electronic transitions can be interpreted as charge transfer from zeolite oxygen lone pair to Ag +. The reaction of H2S with activated Ag+-loaded zeolite A leads to the formation of quantum-sized, luminescent silver sulfide clusters inside the zeolite cavities. The cluster size can be varied by adjusting silver loading.
178
14-O-05 - Elucidating the nature and reactivity of cobalt ions in CoAPOs. A combined FTIR and EPR study of NO and NO2 adsorbed at 77K and 298K E. Gianotti a, M.C. Paganini a, G. Martra a, E. Giamello a, S. Coluccia a and L. Marchese b aDip. di Chimica IFM, Universith di Torino, Italy;bDip, di Scienze e Tecnologie Avanzate, Universit~t del Piemonte Orientale "A. Avogadro ", Alessandria, Italy- [email protected] A combined FTIR and EPR study, using NO and NO2 as molecular probes of the nature and reactivity of cobalt ions in microporous cobalt-aluminophosphates with chabasite-related structure (CoAPO-18 and CoAPO-34) has been performed both at 298 K and 77 K. CoAPOs materials were prepared by following a facile route during which the cobalt ions were directly inserted in the synthesis gels.
2 9 - New Approaches to Catalyst Preparation
(Friday pro)
29-O-01 - The catalytic performance of zeolite ERS-10 C. Perego, M. Margotti, L. Carluccio, L. Zanibelli and G. Bellussi EniTecnologie S.p.A., Via Maritano 26, 20097 San Donato Milanese (MI) Italy Zeolite ERS-10 has been characterised as acid catalyst for ethylbenzene(EB) disproportionation and benzene alkylation. In the disproportionation of EB, ERS-10 shows some similarity with ZSM-12. In the alkylation of benzene with propylene a peculiar behaviour is related to the by-production of diisopropylbenzenes (DIPBs). Like ZSM-5 and ZSM-12, the preferred isomer produced by ERS-10 is the para. A Spaciousness Index (SI) = 5.3 and the preferred formation ofp-DIPB seem to indicate that the effective pore-width of ERS-10 is in the intermediate range between large and medium pore zeolites.
2 9 - 0 - 0 2 Towards total hydrophobisation of MCM-41 type silica surface T. Martin, A. Galameau, D. Brunel, V. Izard, V. Hulea, A.C. Blanc, S. Abramson, F. Di Renzo and F. Fajula Laboratoire des Matdriaux Catalytiques et Catalyse en Chimie Organique- UMR-5618-CNRS -ENSCM, MONTPELLIER - France. brunel@cit, enscm.fr Refinement of the procedure for MCM-41 surface functionalisation was studied with various octylsilanes in order to obtain a maximum surface coverage. Two different types of surface modification using different grafting agents were performed on MTS samples. MTS samples possessing three different pore sizes were functionalised by hydrolysis and polymerisation of pre-adsorbed monolayer of octylsilanes on MTS surface or by chlorine substitution from chlorooctylsilane with nucleophilic assistance. The effect of various experimental parameters on the hydrophobicity and the grafted chain loading was analysed.
179
2 9 - 0 - 0 3 - Novel Lewis-acid catalysts (NLACs): their properties, characterisation and use in catalysis M.H. Valkenberg, C. deCastro and W.F. Hoelderich*
Department of Chemical Technology and Heterogeneous Catalysis, University of Technology RWTH Aachen, Aachen, Germany Different methods for the preparation of Novel Lewis-Acid Catalysts (NLACs) consisting of ionic liquids immobilised on mesoporous support materials are presented. The focus will be placed on materials bound to the carrier via the organic cation of the ionic liquid, either by grafting or by the preparation of organically modified HMS. After addition of aluminium(III)chloride the materials were used as catalysts e.g. in Friedel-Crafts alkylations, in which they displayed high activities and selectivities.
2 9 - 0 - 0 4 - A controlled dispersion of A! 3+ onto a silica m e s o p o r o u s material. A comparative study with A! 3§ incorporation O. Collart (a), A. Galarneau (b), F. Di Renzo (b), F. Fajula (b), P. Van Der Voort (a) and E.F. Vansant (a)
a Laboratory of Adsorption en Catalysis, Department of Chemistry, U.I.A., Universiteitsplein 1, Wilrijk, Belgium - [email protected]," b Laboratoire de Matdriaux Catalytiques et Catalyse en Chimie Organique, ENSCM, Montpellier, France A pure silica MCM-48 is activated by a controlled dispersion of A1 onto the substrate surface performed by anchoring of the Al(acac)3 complex onto the surface silanols. A calcination step removes the organic ligands. The characteristics of the final structure are evaluated by comparison with A1 incorporated MCM-48. The type and concentration of Lewis/Bronsted acid sites is investigated by the adsorption of NH3 and CDBCN.
0 8 - Syntheses with Non-Ionic Surfactants (Friday pm) 08-O-01 - M e s o p o r o u s M S U - X silica tuned for filtration and chromatography applications C. Boissi6re, A. Larbot and E. Prouzet*
Institut EuropOen des Membranes, L.M.P.M. (CNRS UMR 5635) C.N.R.S., 1919 Route de Mendes, F-34293 Montpellier cedex 5, FRANCE. e-mail ."[email protected] Mesoporous MSU-X silica was synthesized with a two-step pathway, that allowed us to get a high control degree on both the final material shape and the porous size distribution. These materials were developed and tested for separating applications, including HPLC chromatography and ultrafiltration membranes. Both applications show that the specific structure of the Micellar Templated Structures exhibits a new behavior in the separation applications, compared with other materials. They are explained by the combined effect of the silica nature and the specific cylindar pore shape.
180
0 8 - 0 - 0 2 - Highly ordered mesoporous silicas synthesis using deca(oxyethylene) oleylether as surfactant: variation of the weight percentage of surfactant and incorporation of transition metal cations G. Herrier and B.-L. Su Laboratoire de Chimie des Mat&iaux Inorganiques, Universitd de Namur, Belgium The synthesis of highly ordered mesoporous silicas using nonionic Cls-lEO10 surfactant has been made by varying the surfactant weight percentages and by incorporation of transition metal ions in the gel. First, the variation of the micellar solution composition leads to reorganization of the phase diagram of micelles and the formation of highly organized hexagonal CMI-3 materials. Second, the role of transition metal cations added during the gel reparation, and the formation mechanism of hexagonally ordered CMI-4 silicas are discussed.
0 8 - 0 - 0 3 - Silica walls of calcined templated by triblock copolymers
mesostructured
SBA-15
materials
M. Imp6ror a and A. Davidson b aLaboratoire de Physique des Solides, UMR 8502-CNRS, e-mail: [email protected] 6Laboratoire de R~activit~ de Surface, UMR 7609-CNRS, e-mail." [email protected] Silica-based SBA-15 materials, synthetised using triblock copolymers as templates, have a 2dimensional hexagonal symmetry. PEO chains are deeply occluded within silica walls of SBA-15 and therefore the density of these walls, after calcination and elimination of PEO chains, may not be uniform. Hydrothermal treatment of SBA-15 can be used to increase their main mesopore diameter and decrease their wall thickness. Unique informations provided by modelling of XRD data complemented by TEM and N2 sorption show that calcined SBA-15 solids cannot be considered as ideal arrays of mesopores imbedded in a uniform silica matrix. The silica walls structure is complex as mesopores appear to be surrounded by a microporous corona of silica. We will also describe how this corona is affected by hydrothermal treatment.
0 8 - 0 - 0 4 - Template / AISBA-15 interaction: double resonance N M R study and consequences on structural properties J.-B. d'Espinose de la Caillerie(a), Y. Yue(b) and A. G6d6on(b) a Laboratoire de Physique Quantique, Ecole Sup&ieure de Physique et de Chimie Industrielles de la Ville de Paris, [email protected],, France b Laboratoire de Chimie des Surfaces, Universit~ Pierre et Marie Curie, France Mesoporous Al-incorporated SBA-15 have been obtained by direct synthesis. The surfactantaluminosilicate interaction during synthesis was studied by double resonance NMR (HETCOR and TRAPDOR) and confronted with the structural properties of the materials obtained after calcination. It is concluded that the microporosity of SBA-15 originates in the partial hydrolysis of the TEOS precursor itself rather than incomplete PEO - silicate phase separation.
181
31 - Environment-friendly Applications of Zeolites (Friday pm) 31-O-01 - Influence of Jordanian chabazite-phillipsite tuff on nutrient concentration and yield of strawberry K.M. Ibrahim (a), A.M. Ghrir (b) and H.N. Khoury (b)
a Dep. of Earth & Env. Sciences, Hashemite University, Zarqa, Jordan, [email protected] b Department of Geology, University of Jordan, Amman, Jordan Chabazite-phillipsite tuff was successfully used as a soil conditioner for planting strawberry under greenhouse conditions for the first time in Jordan. The zeolitic tuff-soil mixture with (2:5) ratio has improved the yield and the height of the plant and has decreased the death percent, the maximum increase in the total yield of the strawberry reaches up to 71.5%. The average gain of the plant height is about 19% and the plant death has decreased to an average of 68%. The results show increase in the nutrient contents except for Mn and Na. The average N gain in the young mature leaves is 39%, whereas in the old leaves is 15.18%.
31-O-02 - Improvements in yield and quality of crops with NASA zeoponic fertilizer delivery systems" turf, flowers, vegetables and grain R.D. Andrews (a) and S.B. Kimi (b)
a ZeoponiX, Inc., [email protected], USA b Malaysian Agricultural Research and Development Institute, [email protected], Malaysia Zeoponic plant growth media and fertility systems developed by NASA and industry consist of (a) plant nutrient ion exchanged natural/synthetic zeolites and (b) synthetic apatite, a phosphorus and trace element fertilizer constituent. Combined, these materials produce superior plant performance in a wide range of commercially important crops, in floriculture, vegetable horticulture, specialty sports turf and important food grains, notably rice. Quality improvements include better germination, higher yields, lower fertilizer requirements, reduced environmental nutrient losses, and better aesthetics in such crops as flowers and sports turf.
3 1 - O - 0 3 - Fe/MFI as a new heterogeneous Fenton-type catalyst in the treatment of wastewater from agroindustrial processes G. Centi, S. Perathoner and G. Romeo
Dip. Chimica Ind. ed Ing. dei Materiali, Univ. Messina, [email protected], Italy A critical issue for a sustainable use of water regards the development of new technologies for the treatment of wastewater from agroindustrial processes. The use of Fe/MFI as a Fentontype heterogeneous catalyst in the wet H202 oxidation of p-cumaric acid, a model compound representative of the phytotoxic phenols present in wastewater from agroindustrial processes, is reported. Aspects analyzed were the effectiveness of the catalyst in comparison with iron salts in solution, the efficiency in the use of H202, the effect of pH, and the behavior of Fe/MFI samples, prepared either by ion exchange or chemical vapour deposition, in relation to activity, by-products and iron leaching. An outline of a possible process flow-sheet is also presented.
182
31-O-04 - Investigation of the storage properties impregnated silica for t h e r m o c h e m i c a l storage of heat
of
zeolites
and
J. J~inchen (a), A. Grimm (a) and H. Stach (b)
a FHTW Berlin, University of Applied Sciences, Berlin, [email protected], Germany b ZeoSys GmbH, Berlin-Adlershof Germany The sorption equilibrium of water in modified zeolites of different types and in silica gels impregnated with hydrophilic salts as well as the texture of the modified silica gels were investigated by thermogravimetry, differential scanning calorimetry, measurements of the isotherms and electron microscopy, respectively. Whereas the modified mesoporous silica materials show a high thermochemical storage capacity because of the high uptake of water the zeolites reveal a better temperature lift since the adsorption equilibrium of the zeolites is shifted toward considerable lower partial pressure. A stepwise hydratation of the salts confined in the pores of the silica gel is correlated with a stepwise curse of the isotherms.
1 3 - F r a m e w o r k s and Acid Sites (Fridaypm) 13-O-01 - W h e r e are the acid sites in zeolites? A novel N M R approach to measure B/Ai ordering around structure directing agents H. Koller a, M. Kalwei a, C. Fild a, R.F. Lobo b, M.A. Camblor c, L.A. Villaescusa d, L. van W011ene
a lnstitut far Physikalische Chemie and Sonderforschungsbereich 458, University of Munster, Manster, Germany," b Univ. of Delaware, USA," c lndustrias Quimicas del Ebro Poligono de Malpica, Zaragoza, Spain," d Univ. of St. Andrews, Scotland; e MPI fur FestkOrperforschung, Stuttgart, Germany The orientation of quaternary ammonium compounds towards the BO4/2-and AIO4/2-groups in a series of as-made zeolites have been determined by 23C{ZH}-IIB REDOR, 13C{1H}-27A1 REAPDOR, and ~H-27A1 REAPDOR solid state NMR. The distribution of acid sites is not random, and a local charge-ordering around monoquaternary structure directing agents (SDAs) is discerned. No such charge ordering was observed for diquaternary SDAs. These methods provide a versatile tool to locate acid sites around the SDA.
13-O-02 - The effect of the nature of heteroatoms (AI, Fe, B) on their distribution in the ZSM-5 structure J. D~de6ek, M. Tudor and J. 12ejka
Academy of Sciences of the Czech Republic, Czech Republic," dedecek@]h-inst.cas.cz The effect of the type of isomorphously substituted atoms (AI, Fe, B) on the number of isolated heteroatoms, their pairs and on the distribution of these pairs in the framework of ZSM-5 structure was investigated using UV-Vis spectroscopy of Co 2+ ions. It was found that the distribution of heteroatoms in the framework of ZSM-5 is not random and depends on the type and concentration of heteroatoms. The number of pairs of boron is significantly lower compared to the number of A1 and Fe pairs for similar concentrations of heteroatoms. All A1, Fe and B pairs are present in three different rings forming, thus, three different sites for divalent cations.
183
1 3 - O - 0 3 - Toward the quantification of aluminum in zeolites using highresolution solid-state NMR C. Fernandez (a), A.-A. Quoineaud (a), V. Montouillout (a), S. Gautier (b) and S. Lacombe (b). a Laboratoire de Catalyse et Spectrochimie, CNRS UMR 6506, ISMRA/Universit~ de Caen, France, b Institut Frangais du Pdtrole, Rueil-Malmaison, France Christian. [email protected] The recent introduction of multiple-quantum NMR (MQMAS), a new high-resolution NMR method facilitates the interpretation of the 27A1NMR spectra of zeolites and thus allows a fast and correct identification of the various aluminum sites. Moreover, this technique yields new information about the structural distortions around the aluminum atoms. The information given by simulation of both MAS and MQMAS leads to the correct quantification of the different sites present in the sample.
13-O-04 - Acidity of ITQ-2 zeolite as studied by FT-IR spectroscopy of adsorbed molecules in comparison with that of MCM-22 B. Onida, F. Geobaldo, L. Borello and E. Garrone Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Turin, Italy, [email protected], it ITQ-2, a novel zeolitic structure prepared by swelling and delaminating a MWW precursor, has been studied by IR spectroscopy. The same precursor yields, when calcined, the zeolite MCM-22. Bronsted acidity has been measured as the propensity either to engage in H-bonds or to transfer the proton to unsaturated hydrocarbons. Comparison with MCM-22 shows that dealumination accompanies the process of delamination, but no appreciable change in residual Bronsted acidity takes place. Reaction of propene with Bronsted sites to branched oligomers occurs mainly on the external surface. Oligomers show no tendency to evolve to allylic cationic species, in contrast with MCM-22.
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Studies in Surface Science and Catalysis 135 A. Galarneau, F. Di Renzo, F. Fajula and J. Vedrine (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
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S U M M A R I E S of P O S T E R P R E S E N T A T I O N S 02 - Zeolite Nucleation and Growth (Monday) 02-P-06 - Epitaxial overgrowth of M A Z onto EMT type zeolite crystals A.M. Goossens (a), V. Buschmann (b) and J.A. Martens (a)
a Centrum voor Oppervlaktechemie en Katalyse, KU Leuven, Belgium johan, martens@agr, kuleuven, ac. be, b FB Materialwissenschaft, TU Darmstadt, Germany. The possibility of growing epitaxial zeolite films on micrometer-sized, structurally different zeolite support crystals was explored with the aim to develop polyfunctional zeolite materials with spatially separated adsorptive and/or catalytic functions. Support crystals of one zeolite type were added to a hydrogel for crystallization of a second zeolite type. Tuning of the crystallization conditions led to the formation of a MAZ-on-EMT overgrowth material consisting of an oriented, continuous film of MAZ crystallites completely covering the surface of the EMT support crystals. The epitaxial relations between the two phases were established using HRTEM and SAED.
0 2 - P - 0 7 - The transformation of Zeolite A and X into nitrate cancrinite under low temperature hydrothermal reaction conditions J.C. Buhl and C. Taake
Institut far Mineralogie, Germany
Universitdt Hannover,
J'Buhl@mineral~176
Investigations on the hydrothermal crystallisation of nitrate enclathrated cancrinite were performed using the alkaline transformation of zeolites A and X at a temperature of 353 K in 2-molar and 16-molar NaOH-solutions. The conversion of the zeolites was followed in the early stage of the reactions for times up to 48 hours by XRD and IR- spectroscopy. A fast and total transformation of zeolite X into cancrinite could be stated in most of the experiments, independent of the alkalinity. In contrast the conversion of zeolite A under low alkaline conditions was slower and accompanied by a sodalite-cancrinite cocrystallisation as well as the formation of an intermediate phase between both structure types. The results indicate a more kinetically controlled reaction mechanism for zeolite A transformation.
02-P-08 - Comparison of crystal linear growth rates for silicalite-I in thermal and microwave syntheses C.S. Cundy and J.O. Forrest
Centre for Microporous Materials, UMIST, [email protected], UK A series of crystal growth experiments has been carded out on reaction mixtures seeded with 43 nm nanocrystals of silicalite-1. For a fixed synthesis composition of 3.1Na20 : 60SIO2 : 6.0TPABr : 5560H20 : 240EtOH, product crystal size was controlled in the range 71-98 nm by varying the quantity of seed crystals added to the synthesis batch. In a comparison between conventional and microwave heating at 100 ~ no significant difference in nucleation or growth behaviour was found between the two methods. Crystal linear growth rates (0.5 A1/At) were the same for all experiments (0.025 + 0.002 ~m h l) and agreed well with published values. Under these experimental conditions, the growing crystals experience the same reaction environment, regardless of the heating method.
186
02-P-09 - Effect of initial hydrogel milling on N a - Z S M - 5 synthesis C. Falamaki (a), M. Edrissi (b) and M. Sohrabi (b)
a Materials and Energy Research Center, P.O. Box 14155-4777, [email protected]., Tehran, Iran b Chemical Engineering Department, Amirkabir University of Technology, Tehran, Iran The effect of milling the initial hydrogel on the synthesis of Na-ZSM-5 using 1,6-hexanediol as structure directing agent has been investigated. In both static and dynamic systems, milling results in a significant increase in the crystal average size and crystal size distribution broadness. Increasing milling time interestingly increases the induction time while the total reaction time decreases with respect to no gel pretreatment. Increasing milling periods simultaneously shift the nucleation curve towards the end of the crystallization process, suppressing it. Milling also increases largely the crystal growth rate; so that increasing the milling time from 24 to 32 h increases the growth rate from 2.71 to 17.07 ~tm h ~. An explanation for the observed results is given.
02-P-10 - Synthesis and c h a r a c t e r i z a t i o n of zeolite Z S M - 2 5 S.B. Hong *a, W.C. Paik a, W.M. Lee a, S.P. Kwon b, C.-H. Shin b, I.-S. Namr and B.-H. Ha d
aChemical Engineering and Technology, Taejon National University of Technology, Korea bChemical Engineering, Chungbuk National University, Korea," CChemical Engineering, Pohang University of Science and Technology (POSTECH), Korea," aChemical Engineering, Hanyang University, Korea The synthesis and characterization of the intermediate-silica zeolite ZSM-25 in the presence of sodium and tetraethylammonium cations is described. The overall characterization results of this study suggest that ZSM-25 is probably an 8-ring or constrained 10-ring pore material containing 4-rings as the smallest structural unit. However, the proton form of ZSM-25 was found to have a poor thermal stability, revealing a serious drawback in its applications as a shape-selective catalyst for acid-catalyzed hydrocarbon conversions.
02-P-11 - A study on the crystallization of a lamellar a l u m i n o p h o s p h a t e A P O - M to a t h r e e - d i m e n s i o n a l a l u m i n o p h o s p h a t e A P O - C J 3 K. Wang, J. Yu, Y. Song, Y. Zou and R. Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun 130023, [email protected], People's Republic of China. An intermediate phase [A12P208][C2H9NO].xH20, denoted APO-M, is crystallized during the formation of three-dimensional open-framework [AlzP2Os][OCH2CH2NH3] (APO-CJ3) in the gel with a molar composition of 2.0 AI('PrO)3:2.8 H3PO4:12.0 ethanolamine: 180 H20. XRD analysis indicates that it has a lamellar structure. It is thermally stable up to 200 ~ The phase transformation from APO-M to APO-CJ3 is investigated by XRD, SEM, ICP, 27A1 and 31p MAS NMR techniques.
187
02-P-12 - Synthesis of nanosized offretite crystals J. Hedlund and E. Kurpan
Division of Chemical Technology, Luleh University of Technology, [email protected], Sweden Colloidal offretite crystals with a maximum size of up to 250 nm were prepared by hydrothermal synthesis at 100~ The system is unusual in the sense that colloidal crystals form from a gel and that the yield sometimes is very high. The effects of the duration of hydrothermal treatment and the composition of the synthesis mixture on the product were investigated using XRD, DLS and SEM. Some syntheses resulted in mixtures of offretite and amorphous material or colloidal sodalite, whereas others resulted in a pure and colloidal offretite product.
02-P-13 - Silicon oxide plays a driving role in the synthesis of microporous SAPO-II Z.-Q. Liu and R. Xu* Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, [email protected], P. R. China. This paper deals with the kinetic study on the synthesis of microporous SAPO-11. It is found that the addition of SiO2 to the starting gel makes the crystallization rate of SAPO-11 fast. The quantitative relationship between the crystallization rate and the amount of SiOz in the starting gel was expressed. Moreover, the relationship between the activation enthalpy in the crystallization of SAPO-11 and SIO2/A1203 in starting gel indicates that a larger SIO2/A1203 decreases the crystallization activation enthalpy, demonstrating that the silicon oxide plays the driving role in the synthesis of SAPO-11.
02-P-14 - Synthesis of nanocrystal zeolite Y and its host effect H. Yang, R. Li*, B. Fan and K. Xie
Institute of Special Chemicals, Shanxi Key Lab of Coal Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China Well-crystallized nanometer-sized zeolite Y of particle size less than 70nm (denoted as nanoY) has been successfully synthesized by a two-step-way and characterized by XRD, TEM, TG-DTA. Its performances as host for metal complex in zeolites have also been studied. The UV-vis spectra, XRD patterns and TG-DTA curves show that [Fe (phen) 3] 2+ has been formed in the supercage of zeolite Y, and higher complex concentration can be obtained in the samples by using nano-Y as host via the 'flexible-ligand' method. [Fe (phen) 3] 2+/nano-Y exhibited higher activities for the liquid phase oxidation of cyclohexane with aqueous H202 than [Fe (phen) 3] 2+/y due to the higher surface area and shorter diffusion pathways.
188
02-P-15- Tailoring crystal size and morphology of zeolite ZSM-5 Ming Liu and S. Xiang*
Department of Chemistry, Nankai University, Tianjin 300071, [email protected], P. R. China Highly crystalline zeolite ZSM-5 with various Si/A1 ratios and two distinct crystal morphology, lath shape and ball shape which appeared as euhedralite or spherulite, with crystal size ranging from 3.7-100/~n and 1.0-62 /.tm were prepared from Na + and K + containing aluminosilicate gels. Approaches for tailoring crystal size and morphology such as seeding, cation effect control, oxyanion addition, aging the precursor gel and lowering alkalinity during the intermediate stage were found applicable. The method of combining aging and lowering alkalinity was proved to be useful for preparing lath-shape euhedralite from a broad range of crystal size.
02-P-16 - Modeling of silicalite crystallization from clear solution K.A. Carlsson, J. Warzywoda and A. Sacco, Jr.
Center for Advanced Microgravity Materials Processing, Chemical Engineering Department, Northeastern University, Boston, MA 02115, USA, [email protected]. A mathematical model of Silicalite crystallization from "clear solution" was developed and solved numerically. Crystallization was considered to be solution-mediated, and to involve three categories of silica species and three steps: activation, nucleation, and crystal growth. Nucleation was represented by a condensation reaction between the hydroxyl groups present on the surface of 10 nm amorphous silica particles and the soluble silica species, producing activated complexes, which transform to crystalline nuclei. Both nucleation and crystal growth were considered to be reaction controlled. The model simulated well the in situ experimental data. This suggests that the hypothesized nucleation mechanism can be used to qualitatively describe the nucleation event during clear solution Silicalite crystallization.
02-P-17 - Interaction/synergistic effect of Mg 2+ and Ba 2+ on the size and morphology of the zeolite L crystals S. Ferchiche, J. Warzywoda and A. Sacco, Jr.
Center for Advanced Microgravity Materials Processing, Chemical Engineering Department, Northeastern University, Boston, MA 02115, USA, [email protected]. The effect of Mg 2§ and Ba2§ added separately and added together on the purity, morphology, and size of the products of zeolite L was investigated. All products were 100% pure zeolite L. The results of a 22 factorial experiment (two factors: gel Mg 2§ and Ba 2§ content) showed a two-factor interaction: the average crystal length depended on the concentration of both cations in the gel, and decreased with the increasing gel cation content. A synergistic effect was observed: the crystals formed with both cations were smaller and their morphology improved from poorly to well formed cylinders compared to crystals obtained by combining products grown using Mg 2§ and Ba2§ added separately at the corresponding concentrations.
189
02-P-I 8 - In-Situ N M R study of mechanisms of zeolite A formation M. Smaihi, S. Kallus and J.D.F. Ramsay LMPM UMR 5635 CNRS-ENSCM-UM2, 1919 route de Mende, 34293 Montpellier Cedex 5, France. smaihi @lmpm. cnrs-mop,fr In-situ liquid-state NMR has been used to follow the first steps of zeolite A synthesis. 27A1 and lac NMR has been used to study the species that occur in solution and the role of tetramethylammonium hydroxide as structure directing agent (SDA). 27AI NMR results indicate that several aluminosilicate species are formed immediately during the first stage of the synthesis reaction. Furthermore, lac NMR results indicate that short-range intermolecular interactions between the SDA and these species occur just after the mixing of silicate and aluminate solutions. These results suggest that small oligomeric species are created which form a cage around the SDA and further A1/Si substitutions occur at the edge of these species.
02-P-19- Effects of synthesis parameters on zeolite L crystallization Y.S. Ko, S.H.Chang and W.S. Ahn + School of Chemical Science and Engineering, Inha University, Inchon, Korea 402-751 , w has ahn@ inha. ac. kr Zeolite L was prepared from a substrate having the molar composition of 5.4K20-5.5Na20A1203-30SiO2-500H20 at temperatures of 373-443K. The influence of synthesis parameters such as starting raw materials, reaction temperature, gel aging, stirring, seeding, heating rate and mixing sequence on the crystallization rate and particle size distribution was investigated. Crystallization rate was promoted by introducing gel aging, seeding, stirring and rapid heating rate. The crystal size could be decreased significantly by stirring the gel during the synthesis or subjecting the substrate mixture to an aging treatment at room temperature.
02-P-20- Some aspects of NU-86 zeolite crystallization S.V. Dudarev a, A.V. Toktarev a, G.V. Echevsky a, C.L. Kibby b and D.J. O'Rear b. ~Boreskov Institute of Catalysis, Ak. Lavrentieva Av. 5, Novosibirsk, 630090, Russia. bChevron Research and Technology Company, 100 Chevron Way, Richmond, CA 94802, USA. Crystallization of wide-pore NU-86 zeolite was investigated using different templates and silica sources, different chemical compositions of the reaction gels, and with or without seeding. It was found that NU-86 zeolite forms best from thick and seeded reaction gels based on Cab-O-Sil fumed silica. Seeding with NU-88 zeolite leads to formation of a pure NU-86 zeolitic phase. Other concurrent zeolitic phases are ZSM-23, mordenite, ZSM-12, and analcime. We found a higher optimum alkalinity for the reaction gel and a lower optimum stirring rate than those reported in the literature.
190
02-P-21 - S y n t h e s i s of zeolite S r , K - Z K - 5 P.C. Russell, S.L. Stuhler, A.L. Kouli, J. Warzywoda and A. Sacco, Jr.
Center for Advanced Microgravity Materials Processing, Chemical Engineering Department, Northeastern University, Boston, MA 02115, USA, [email protected]. Zeolite Sr,K-ZK-5 (KFI) with purity >95% was grown statically in Teflon-lined autoclaves at 100-150 ~ Reaction composition diagrams showed that Sr,K-ZK-5 crystallizes as a nearly pure phase in a narrow composition range in which the variations of A1203, SiO2, and K20 must be held to less than 10 tool%. Four impurity phases were identified: zeolites L (LTL), T (ERI), W (MER), and chabazite-type (CHA). Crystallization curves showed that the time to obtain a fully crystalline Sr,K-ZK-5 increased from ~80 to ~100 h with the gel SiO2 content increasing from 75.5 to 77 mol% and from ~80 to ~280 h with the synthesis temperature decreasing from 150 to 100 ~ Attempts to obtain pure Sr,K-ZK-5 by seeding, aging, the use of different sources of Si and A1, and the use of stainless steel autoclaves were not successful.
0 2 - P - 2 2 - E v i d e n c e for in-situ directing syntheses J.C. Vartuli, G.J. Kennedy, B.A. Yoon and A. Malek
agent
modification
in zeolite
ExxonMobil Research and Engineering, Corporate Strategic Research, Annandale, NJ 088013059, USA, J C [email protected] ZSM-22 (TON) can be produced from potassium based 1,6 hexamethylenediamine synthesis mixture, while, ZSM-34 (an OFF/ERI intergrowth) is synthesized from the same synthesis mixture with the addition of sodium. NMR analyses of the as-synthesized zeolite samples indicated the presence of a carbonyl species in all of the ZSM-34 samples, but not in any of the preparations that produced ZSM-22. The carbonyl species was present only after the synthesis mixture was heated above ambient temperature. Molecular modeling studies calculated a favorable fit of the carbamic species within the pore system of the Erionite suggesting a reason for the formation of the OFF/ERI intergrowth.
0 2 - P - 2 3 - T h e influence of different silica sources on the crystallization kinetics of zeolite beta W. Schmidt (a), A.V. Toktarev (b), F. SchtRh (a), K.G. Ione (b) and K. Unger (c)
a MPIfiir Kohlenforschung, Mtilheim, w~ Germany b Institute of Catalysis, Academy of Sciences of Russia, Novosibirsk, Russia c Institutf~r Anorganische Chemie, Johannes Gutenberg- Universitcit, Mainz, Germany Zeolite beta was synthesized with different silicon sources. The dissolution of the silicon sources and the reaction temperature obviously determined the crystallization rate of the zeolite. Silica sol reacted rapidly at 110, 140, and 170~ while fumed silica and TEOS only reacted readily at 170~ The aluminum content in the reaction gel determined the termination of the crystal growth, after all aluminum was consumed, the crystal growth stopped. The acidic properties of the obtained materials were very similar, but a significant influence of the silicon source on the particle size of the resulting zeolite was observed.
191
02-P-24 - Population balance: a powerful tool for the study of critical processes of zeolite crystallization B. Subotic, T. Antonid and J. Bronid Rudjer Boskovic Institute, P.O.Box 180, Bijenicka c. 54, HR-10 001 Zagreb, Croatia
subotic@rudjer, irb.hr A new insight in the population balance of zeolite crystallization is given, by introduction of new functions of nucleation and crystal growth as well as the correction of the crystal growth curves by introduction of the heating function of the reaction mixture. The modified population balance is used for the analysis of the critical processes (nucleation and crystal growth of zeolite) during crystallization of zeolites A, X and ZSM-5.
02-P-25- Synthesis of TMA-SOD from a novel type layered silicate by solid state transformation 9
.a
9
.a
Y. Klyozuml , F. Mlzukaml , Y. Akiyama b, T. Ikeda c and T. Nishide d
aNational Institute of Materials and Chemical Research, I-I Higashi, Tsukuba 305-8565 Japan, kiyozumi@nimc,go.jp bAmersham Pharmacia Biotech, 3-25-1 Hyakuninchou, Shinjuku-ku, Tokyo 169-0073 Japan, CNational Institute for Research in Inorganic Materials, Tsukuba, Ibaraki 305-0044 Japan, dNihon University, Dep. of Materials Chemistry and Engineering, Koriyama 963-8642 Japan, TMA-SOD was synthesized from a novel type of layered silicate (HLS) by solid state transformation. HLS was easily converted to the TMA-SOD by mixing it with NaAIO2 and heating at 70 - 150~ for 3 - 24h even without addition of HzO as the solvent. NaAIO2 is inserted into the HLS layers, that is, the-Si(OSi)3 (Q3) sheets, and accelerates the cleavage of the sheets into certain building units which subsequently form SOD structure. It was found that the obtained TMA-SOD becomes dark blue under X-ray irradiation indicating TMA + and Na43+ cluster are occluded within the SOD cage.
02-P-26- Direct conversion of bulk-materials into MFI Zeolites by a bulkmaterial dissolution technique S. Shimizu (a)(b) and H. Hamada (e)
a Joint Research Center for Harmonized Molecular Materials, Japan Chemical Innovation Institute, [email protected], Japan b Advanced Technology Laboratory, Kubota Corporation, [email protected], Japan c National Institute of Materials and Chemical Research, [email protected], Japan By using a novel synthetic technique named DBMD, we succeeded in converting glass bulk materials by replacing the glassy part to MFI zeolite crystals from the surface to the inside. A thoroughly converted zeolitic tube and partially converted zeolitic fibers and fabric were prepared with this technique. Seed crystals accelerated crystallization and improved both coverage and uniformity of the crystals.
192 0 2 - P - 2 7 - Synthesis of a new microporous silicate using DABCO-based
structure-directing agent Y. Kubota a, J. Pl~vert b, T. Honda a, P. Wagner c, M.E. Davis c, T. Okubo b, Y. Goto d, Y. Fukushima e and Y. Sugi a
aGifu University, Gifu 501-1193, Japan, kubota@apchem, gifu-u.ac.jp, sugi@apchem, gifu-u, ac.jp bThe University of Tokyo, Tokyo 113-8656, Japan CCalifornia Institute of Technology, Pasadena, CA 91125, U S. A. dJapan Chemical Innovation Institute, 12-3-5 Kandajimbocho Chiyoda, Tokyo 101-0051, Japan eToyota Central R&D Labs., Inc., Nagakute, Aichi 480-1192, Japan A new zeolitic phase (GUS-1) is synthesized by hydrothermal method from all-silica synthesis mixture using 1,1'-butylenedi(4-aza-l-azonia-2,5-dimethylbicyclo[2.2.2]octane)as SDA. Results of the synthesis and structure-determination are described. The behavior of the SDA during synthesis is also discussed.
02-P-28 - Heteroepitaxial structures
connection
of zeolites with
different
pore
T. Wakihara a, J. P16vert a, S. Nair b, M. Tsapatsis b, S. Yamakita a, Y. Ogawa a, H. Komiyama a, M. Yoshimura c, M.E. Davis a and T. Okubo a'c
a. The University of Tokyo, [email protected], Japan. b. University of Massachusetts, Amherst, US.A c. Tokyo Institute of Technology, Yokohama, Japan d. California Institute of Technology, Pasadena, U.S.A e. PRESTO, JST, Japan Some zeolite structures are composed of repeated sequences of layer stacking. By controlling the sequences, novel structures can be constructed. In this paper, ABC 6-member ring zeolites are grown on millimeter-sized sodalite single crystals. Cancrinite with one-dimensional channels and chabazite with three-dimensional intersections are selected as the overgrown species. As a result, the first in-plane and out-of plane oriented cancrinite films are obtained. In the case of chabazite, the textured planes with axis symmetry on sodalite substrates are formed.
02-P-29 - Study of zeolite A crystallization from clear solution hydrothermal synthesis and population balance simulation
by
J. Bronic a, P. Frontera b, F. Testa b, B. Subotic a, R. Aiello b and J. B.Nagy c
a) Ruder Boskovic Institute, Zagreb, [email protected], Croatia; b) University of Calabria, Rende, Italia; c) Facultes UniversitairesNotre-Dame de la Paix, Namur, Belgium The influence of real time temperature increase from ambient to synthesis temperature precursor ageing, and crystallization temperature, was studied on crystallization of zeolite A from the clear solution under static conditions. Phase composition, crystal size, mass and morphology were followed using various experimental techniques such as XRD, SEM, LLS, and NMR. Simulation of the nucleation and crystal growth processes was made adopting population balance model for synthesis from clear solution. Correlation of the measured and simulated (calculated) data gives very good agreement.
193
02-P-30 - Synthesis of zeolite SSZ-35 using N-methyl hexahydrojulolidinium salt as a new family of structure-directing agents (SDAs) Y. Kurataa , T.-A. Hanaoka b and H. Hamada b Japan Chemical Innovation Institute (JCII), Tsukuba, Ibaraki 305-8565, Japan b National Institute of Materials and Chemical Research, Tsukuba Ibaraki 305-8565, Japan Three isomers of N-methyl hexahydrojuladinium salts were successful in preparing molecular sieves for the first time. When they were used as structure-directing agents (SDAs), they gave rise to the synthesis of three molecular sieves, SSZ-35, SSZ-31 and RUB-13. The stereoconfigurations of these organics are supposed to be an extremely important factor.
02-P-31 - The fitting equation for zeolite crystallization with seeds A.V. Toktarev and S.V. Dudarev Boreskov Institute of Catalysis, Ak. Lavrentiev Av. 5, Novosibirsk, 630090, Russia. The simple two-parametric equation for fitting the crystallization curve of zeolite in the presence of seeds is proposed. The equation is genetically related with Avrami-Erofeev equation and has the following expression, x = 1- exp[-k• Applicability of the proposed equation was verified by examples on ZSM-5 and NaA crystallization with MFI and LTA type seeds, respectively.
02-P-32 - Influence of the thermal treatment of the aluminosilicate gel precursor on the zeolite nucleation C. Kosanovi6, B. Suboti6 and D. Kralj Ruder BogkoviO Institute, Bij'enidka 54, 10000 Zagreb, Croatia cleo@rudjer, irb. hr Solid phase (X-ray amorphous aluminosilicate) separated from the hydrogel having the batch composition 3.23 Na20'A1203'l.93 SIO2"128 H20, was calcined at different temperatures (100-800~ for l h and then transformed into zeolite A by heating in a 2M NaOH solution at 80~ Analysis of both precursors and products (zeolite A) has shown that the calcination of the precusor lowers the concentration of nuclei in the gel matrix and hence influences the particulate properties of the zeolite obtained during the hydrothermal treatment of the precursors
194
02-P-33 - Efficient co-templating roles of amines and amides a d m i x e d with a l k y l a m m o n i u m salts for the stabilisation of new A I P O 4 - n topologies C. Borges(a), M.F. Ribeiro(a), C. Henriques(a), M.T. Duarte(a), J.P. Louren~o(b) and Z. Gabelica(c) a Instituto Superior TOcnico, Lisboa, Portugal; e-mail.'filipa.ribeiro@ ist.utl.pt b Universidade do Algarve, 8000 Faro, Portugal CGSEC, ENSCMu, Univ. de Haute Alsace, Mulhouse, France Two different aluminophosphate structures were synthesised in aqueous media using as main template methylamine (MA), directly added, ,or generated in situ from methylformamide (MF). Both involve novel A1PO4-n topologies that undergo structural transformations upon template removal, yielding above 350~ microporous thermostable materials with interesting properties. Tetraalkylammonium (TEA) cations were used optionally as co-templates along with MA. Only non protonated MA was found incorporated into the pore volume. TEA appeared to stabilise one of the phases during nucleation and/or growth processes.
02-P-34 - Static synthesis of zeolite M C M - 2 2 Y.-M. Wang, X.-T. Shu 2and M.-Y. He Research Institute of Petroleum Processing, China Petrochemical Corporation, [email protected], P. R. China Zeolite MCM-22 has been synthesized as a pure phase and with good crystallinity under static conditions by using either two-step method or a seeding method. In the two-step method an initial crystallization step at a much higher temperature (at least higher than 443K) makes it possible to statically synthesize a high-quality MCM-22, which considerably reduces the time for crystallization and the consumption of the organic template. And in this method the silica sources with lower surface areas (less than 500 mZ/g) can yield zeolite MCM-22. Also the directing-gel prepared at a higher temperature similarly has the desired effect on the static synthesis of MCM-22, and the aging step can be left out in this method.
02-P-35 - Synthesis of pure silica Beta by the conventional h y d r o t h e r m a l method W. Guo, J. Yao, Y. Luo and Qi. Li* Department of Chemistry, Fudan University, Shanghai 200433, P. R. China [email protected] Pure silica Beta has been crystallized from alkali-free hydrogel containing tetraethylammonium hydroxide and fumed silica at 413 K by the conventional hydrothermal synthesis method. Characterization has been done by XRD, IR, SEM, solid-state NMR, thermal analysis and N2 adsorption. The results show that a highly crystalline pure silica Beta is formed. 29Si MAS NMR reveals that the pure silica Beta has a small number of Q3 sites originating from structural defects and almost half of Q3 sites are silanol groups. Thermal analysis shows that pure silica Beta possesses nonequivalent Q3 sites that are siloxy groups counterbalanced by TEA + cations.
195
02-P-36- Hydrothermal transformation of a layered silicate, Na-magadiite, into mordenite zeolite T. Selvam and W. Schwieger*
Institute of Technical Chemistry I, University of Erlangen, D-91058 Erlangen, Germany wilhelm, schwieger@rzmail, uni-erlangen, de Hydrothermal transformation of a layered silicate, Na-magadiite, into a commercially important mordenite zeolite is achieved, at 175 ~ using tetraethylammonium hydroxide as the intercalating and/or structure directing agent. Samples were characterized by XRD, IR, SEM, DTA and N2 adsorption measurements. The results indicate that the mordenite samples obtained by this new route are highly crystalline, more uniform and smaller in size (0.1-0.2 ~tm).
02-P-37 - In-situ diagnostic of zeolite crystal growth by real time ultrasound monitoring R. Herrmann(b)*, W. Grill(c), T.J. Kim(c), O. Scharf(b), R. Schertlen(d), M. Schmachtl(c), W. Schwieger(b), C. Stenzel(a), H. Toufar(e) and Y. Venot(d) a Astrium GmbH, b University Erlangen, c University Leipzig, d University Karlsruhe, e Tricat Zeolites GmbH- Technical Chemistry 1, University Erlangen, Egerlandstr. 3, D91058 Erlangen, Germany - e-mail. ralph.herrmann@rzmail, uni-erlangen.de
The aim of the present work is the detection of characteristic changes in synthesis gels of different zeolites by the measurement of variations of the attenuation and the sound velocity of ultrasonic waves traveling in the reaction fluids. For the zeolites A and X characteristic changes of the measured ultrasound signals correlating with the processes of gel formation and zeolite crystallization were observed. It could be shown, that the used ultrasound monitoring is capable to demonstrate aging effects of the mixtures and to observe the onset of fast crystal growth, which was verified by ex-situ XRD analysis. The real-time in-situ USdiagnostic is a new promising tool for zeolite crystallization and it is also feasible under microwave heating conditions.
02-P-38- Effect of ageing on the decomposition of tetra-alkylammonium ions as studied by microwave heatin~2 2 TM
A. Ararat l, H. van Bekkum, T. Maschmeyer and J.C. Jansen 2.
1- Chemistry Department, Faculty of Science, Helwan University, Ain Helwan, Cairo, Egypt. 2- Laboratory of Applied Organic Chemistry and Catalysis, Delft University of Technology, Delft, The Netherlands. Extremely fast decomposition of tetraalkylammonium salts in freshly prepared aqueous alkaline solutions was observed upon immediate heating of the solutions, whereas no decomposition was observed in aged solutions. This is of importance when zeolite synthesis under fast heating conditions such as microwaves is performed. The decomposition reaction is initially first order in the hydroxide concentration and comes to completion due to OHconsumption. The results are discussed in terms of the formation of water-clathrate-like structures around the alkylammonium groups upon ageing of the starting solutions.
196
02-P-39 - Synthesis of siliceous mordenite from system free of amine X. Qi, x. Liu and Zhan Wang Research Institute of Beijing Yanshan Petrochemical Corporation, 102500, [email protected], China The stability phase domain to give mordenite in the absence amine but with fluoride was investigated. As compared with the system without fluoride, the domain producing mordenite is broadened and the area leading to quartz is reduced. ZSM-5 and ferrierite are no longer formed. The action of fluoride anion to favor the crystallization of mordenite is clearly shown. When F/SiO2 ratio is above 0.10, the SIO2/A1203 ratio of product increases with the F/SiO2 ratio and quartz is no longer formed. The results clearly show the strong action of fluoride anion in directing the system towards the formation of siliceous mordenite.
02-P-40 - High-resolution solid state MAS NMR studies on the role of promoter (phosphate) in the nucleation and crystallization of Silicalite-1 (Si-MFI) P.R Rajamohanan a, P. Mukherjee b, and S. Ganapathy a and R. Kumar b aPhysical Chemistry Division, National Chemical Laboratory, Pune - 411 008, India bCatalysis Division, National Chemical Laboratory, Pune - 411 008, India With the help of multinuclear solid state NMR experiments, the promoter (phosphate) induced acceleration of zeolite formation is proved unambiguously. It is proposed that the hydration spheres of the silicate units formed by the hydrolysis of the tetraethyl ortho silicate (TEOS) will be modified as part of the water molecules will be taken away by the promoter. This will speed up the process of the association of Ql, Q2, and Q3 units to form more Q4 units in the gel, leading to the formation of secondary building units at a faster rate. The promoter can also enhance the assembling of the SBU's in the similar way.
02-P-41 - The influence of concentration on the structure-directing effects of diethylenetriamine in the synthesis of porosils P. Behrens, V.J. Hufnagel and A.M. Schneider Institut fiir Anorganische Chemie, Universitcit Hannover, Callinstrafle 9, D-30167 Hannover, Germany," E-mail. Peter.Behrens@ mbox.acb.uni_hannover.de Various parameters are known to influence the kinetically controlled synthesis of silica-rich zeolites and related compounds such as porosils. In syntheses where diethylenetriamine is acting as a structure-directing agent (SDA), different porosil structures can crystallize: nonasil, ZSM-48, silicalite-1 and an unknown structure. The type of porosil obtained is found to depend upon the concentration of the SDA, i.e. upon the compositional ratio between diethylenetriamine and water in the synthesis gel. The results can be rationalized on the basis of the structural arrangements of the diethylenetriamine molecules in the porosil formed. These arrangements are influenced by the competition between intramolecular hydrogen bonds within individual diethylenetriamine molecules, by the ability to form intermolecular hydrogen bonds between the molecules of the SDA and by the solvation of these molecules by water.
197
02-P-42- Synthesis of high-silica MWW zeolite L.M. Vtjurina, S.S. Khvoshchev and I.V. Karetina
Coming Scientific Center in St.Petersburg, [email protected], Russia The synthesis and characterization of pure and highly crystalline MWW are reported. Using silica sole as SiO2 source allows to obtain the MWW crystals with SIO2/A1203 = 80 at the static synthesis conditions without preliminary aging. Adsorption data for Ar at 77 K and C6H6 at ambient temperature on MWW with SiOJA1203 -- 80 are given. Thermostability of MWW increases with increasing SIO2/A1203 ratio. Adsorption of NO on MWW zeolites is considerably influenced by the nature of cations.
198
06 - Fundamentals of Micelle Templating (Monday) 06-P-05 - X-ray diffraction analysis of ordered mesoporous silica M. Ookawa (a), Y. Yogoro (a), T. Yamaguchi (a) and K. Kawamura (b)
a Department of Applied Chemistry, Ehime University, Matsuyama, [email protected], Japan," b Department of Earth and Planetary Sciences, Tokyo Institute of Technology, Japan The analysis of wall structure of MCM-41 prepared under acidic or basic condition was attempted by X-ray diffraction (XRD) using Mo Kc~. The profiles of XRD in the wide angle region for MCM-41 were similar regardless preparation methods. The significant difference was shown in profiles of XRD and interference function of silica glass and MCM-41. Correlation function suggests that pore wall of MCM-41 prepared under acidic condition have a structure of narrow Si-O-Si angle compared with MCM-41 prepared under basic condition or silica glass.
0 6 - P - 0 6 - Active MCM-48 supported catalysts" different strategies to increase the structural and chemical stability P. Van Der Voort, M. Mathieu and E.F. Vansant
University of Antwerpen (U.I.A.), Dept. of Chemistry, pascal, [email protected], Belgium Several strategies have been developed and compared to increase the mechanical and hydrothermal stability of pure silica MCM-48. A thickening of the walls, using SiCI4 and water, results in a wall thickening of 50% and strongly improves the mechanical stability of the samples. A partial hydrophobization with an amphiphilic silane, such as dimethyldichlorosilane, has extremely beneficial effects on the thermal, mechanical and hydrothermal stability of the samples and strongly reduces the leaching of the active centers. Both wall thickening and hydrophobization can be combined into one simple post-synthesis treatment. Such treatments will be necessary to allow a practical (industrial) use of the MCM-48 support as catalysts support or adsorbent.
06-P-07 - Strong acidic and high temperature hydrothermally mesoporous aluminosilicates with well-ordered hexagonal structure
stable
Zo. Zhang (a), Y. Han (a), R. Wang (a), S. Qiu (a), D. Zhao (b) and F.-S. Xiao (a*)
a Dept. of Chem., Jilin Univ., Changchun 130023,[email protected], China. b Dept. of Chem., Fudan Univ., Shanghai 200433, China. Strong acidic and high temperature hydrothermally stable mesoporous aluminosilicates with well-ordered hexagonal structure (MAS-5) have been successfully synthesized from assembly of pre-formed aluminosilicate precursors with cetyltrimethylammonium bromide (CTAB) surfactant. The MAS-5 shows extraordinary stability both in boiling water (over 300 h) and in steam (800~ for 2 h). Temperature programmed desorption of NH3 shows that acidic strength of MAS-5 is much higher than that of MCM-41.
199
06-P-08 - Studies on the synthesis of A I - M C M - 4 1 m e s o p o r o u s materials G.A. Eimer, L.B. Pierella and O.A. Anunziata
CITeQ(Centro de lnvestigaci6n y Tecnologia Quimica), Facultad C6rdoba. Universidad Tecnol6gica Nacional. CC36 (5016) C6rdoba. Argentina. Tel-FAX.'54-351-4690585 email :[email protected], utn. edu.ar The novel synthesis method of AI-MCM-41, using tetraethoxysilane (TEOS) and sodium aluminate (NaA102) as Si and A1 sources, was studied. Dodecyltrimethyl ammonium bromide was employed as template and the initial gel was hydrothermally treated at 100~ The influence of reaction conditions such as surfactant/Si molar ratio and synthesis time have been evaluated. The samples showed well-defined X-ray diffraction patterns indicating a highly ordered structure of pore arrays. MCM framework was characterized by infrared analysis and a tentative assignment of bands was performed. Both XRD and FT-IR studies could be correlated and an optimal characterization of material could be reached.
06-P-09 - Controlled synthesis of microporous and m e s o p o r o u s silica-based molecular sieves in the presence of d o d e c y l d i m e t h y l b e n z y l a m m o n i u m chloride Z.Y. Yuan (a), W. Zhou (b), L.M. Peng (a), J.-Z. Wang (c) and H.X. Li (c)
a Be~'ing Laboratory of Electron Microscoscopy, Chinese Academy of Sciences, Beijing [email protected], P.R. China, b School of Chemistry, University of St. Andrews, St. Andrews, UK, c Department of Chemistry, Nankai University, Tianjin, P.R. China Microporous silicas with pore size of 12.2 A were prepared by either S+XI + or S+I pathways at room temperature using dodecyldimethylbenzylammonium chloride (DDBAC) surfactant. The pore size of the synthesized materials could be tuned from microporous to mesoporous range by the crystalline temperature or using mixed surfactants of DDBAC and cetylpyridinium chloride. The pore structure can transfer from disordered tubular array to ordered hexagonal phase by the increase of the molar ratio of CPC1 to DDBAC.
06-P-10 - F o r m a t i o n of d o u b l e - m e s o p o r e silica and its transformatoin into MCM-41 X.-Z. Wanga,T. Doua,y.-z. Xiao a and B. Zhong b
~Institute of Special Chemicals, Taiyuan University of Technology. Taiyuan 030024 China bState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, the Chinese Academy of Sciences. Taiyuan 030001 China The influence of alkali/silica molar ratio in the synthesis of mesoporous molecular sieve materials was studied in a simple synthesis system containing tetraethylorthosilicate, water, alkali and the cetyltrimethylammonium bromide at room temperature. The resulting silicate materials were characterized by XRD, 29Si MAS NMR, TEM and N2 adsorption-desorption isotherms. The results suggest that the formation of different surfactant-silicate aggregation array morphology not only relies on an interaction between silicate ions and the surfactant, but also on a proportion of the silicate species to surfactant.
200
06-P-11 - The synthesis and hydrothermal stability of directly usable hexagonal mesoporous silica by efficient primary amine template extraction in acidified water K. Cassiers, P. Van Der Voort and E.F. Vansant
Dept. of Chemistry- Laboratory of Adsorption and Catalysis, University of Antwerp (U.I.A.), Universiteitsplein 1, B-2610 Wilrij'k, Belgium, e-mail: [email protected] High quality HMS was repeatedly and reproducibly prepared by a novel extraction procedure to remove the primary amine template using acidified water. This very efficient extraction (100%) does not affect the physical properties of the resulting mesostructure. Compared to the ethanol-extracted HMS, no subsequent calcination step is required to remove the surface ethoxy groups produced during the ethanol extraction. Moreover, the recovered surfactant can be easily re-used in a fresh synthesis. Furthermore, an improved hydrothermal stability was observed after using the acidified water extraction procedure.
06-P-12 - Synthesis and characterization of highly ordered chromiumsubstituted MCM-48 materials with tailored pore sizes C. Pak and G.L. Hailer
Department of Chemical Engineering, Yale University, P.O. Box 208286, New Haven, CT 06520-8286, USA Cr-substituted MCM-48 materials have been prepared by a direct hydrothermal procedure using mixtures of cationic alkyltrimethylammonium surfactant with different alkyl chain length and neutral surfactants. At least eight X-ray diffraction peaks corresponding to the cubic Ia3d structure and high surface areas were observed for all the samples, which indicates that the Cr containing materials have a highly ordered MCM-48 structure. Average pore size of Cr-MCM-48 samples was increased from 3.2 to 3.9 nm with increasing alkyl chain from 14 to 18 carbons. It is suggested from an intense pre-edge peak in the XANES that the Cr in the MCM-48 structure has tetrahedral coordination. -
06-P-13 - Preparation and characterization of mesoporous silica spheres R. Van Grieken, D.P. Serrano, C. Martos and A.M. Melgares
ESCET. Universidad Rey Juan Carlos, c/Tulipdn s/n, 28933 M6stoles, Madrid, Spain. e-mail: r. vangrieken@escet, urjc. es The effect of different variables in the preparation of mesoporous silica spheres has been investigated through a two-phase method that requires tetrabutoxy silane as silica source, cetyltrimethylammonium chloride as surfactant, and water as solvent. The materials synthesized show regular pores with sizes around 2.0 nm, BET surface areas larger than 1000 m2/g and a narrow spherical particle size distribution. These textural properties are achieved through the surfactant removal by a mild calcination procedure, otherwise the porous structure is partially destroyed. The size of the silica spheres so obtained can be controlled in the range 300-700 pm through different variables, mainly by varying the stirring speed of the two-phase solution.
201 0 6 - P - 1 4 - Rapid synthesis of high quality MCM-41 silica via ultrasound
irradiation X.-H. Tang (a,b), Ya. Wang (a), W. Huang (a,b), S. Liu (a,b), O. Palchik (a), E. Sominski (a), Y. Koltypin (a) and A. Gedanken (a)
a Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, [email protected], il, Israel b College of Chemistry, Nankai University, Tianjin 300071, P. R. China High quality MCM-41 silica has been sonochemically synthesized in a relatively short time and characterized by XRD, TEM, 29Si MAS NMR, nitrogen sorption and hydrothermal treatment. It reveals that ultrasound promotes the condensation of surface silanol groups among micelles and accelerates the formation of MCM-41 framework. The as-synthesized MCM-41 silica, whose pore size shows a very narrow distribution, possesses a thicker wall and enhanced thermal stability as compared to those prepared with conventional methods.
0 6 - P - 1 5 - Synthesis of mesoporous aluminosilicate FSM-materials derived from synthetic and natural Saponite. T. Linssen (a), M. Barroudi (a), P. Cool (a) and E.F. Vansant (a)
a Laboratory of Adsorption and Catalysis, Univ. of Antwerp (U.I.A), [email protected] A new successful synthesis route for the preparation of FSM-16 is developed using leached Saponite, in combination with cetyltrimethyl ammoniumbromide [CI6Ha3N+(CH3)3Br or CTMA+Br ] as structure directing agent. Acid treatment of the clays allows the formation of mesoporous aluminosilicate hexagonal structures (M41S family) with high porosity (max. 0.6 cc/g), high specific surface area (max. 900 cc/g), high pore wall thickness, a narrow pore size distribution and uniform pore size distributions. Using natural clays as silica source is of great interest in an economical and ecological way while the aluminium present in the clay and finally in the mesoporous structure is an additional advantage looking to acid catalysis.
06-P-16 48
- 129Xe
NMR and adsorption studies of Si-MCM-48 and Al-MCM-
G. Oye (a), M.-A. Springuel-Huet (b), J. Fraissard (b), M. St/3cker (c) and J. Sj~blom (d)
a Department of Chemistry, University of Durham,, Durham, UK b Laboratoire Chimie des Surfaces, ESA 7069, Universitd P. et M. Curie, Paris, France c SINTEF Applied Chemistry, Blindern, Oslo, Norway d Statoil A/S R&D Centre, Rotvoll, Trondheim, Norway Si-MCM-48 and A1-MCM-48 materials have been investigated by means of 129Xe NMR spectroscopy and gas adsorption measurements. The chemical shift of adsorbed Xe in these samples is found to be in the same range as for MCM-41 materials. Furthermore, A1-MCM-48 shows a higher chemical shift and a broader line width compared to Si-MCM-48. This might be due to specific Xe-AI interactions or to interactions of Xe with a more irregular surface.
202
06-P-17 - 27Al-NMR studies on A I - M C M - 4 1 molecular sieves synthesized with different Si/A! ratios and different a l u m i n u m sources W. BOhlmann and D. Michel
University of Leipzig, Faculty of Physics and Geosciences, LinnOstr. 5, D-04103 Leipzig, Germany, e-mail. bohlmann@physik uni-leipzig, de AI-MCM-41 molecular sieves in there sodium and hydrogen form with different Si/A1 ratios (16...256) were synthesized using aluminum sulfate and aluminum triisopropylate as source. In all experiments the pH value was held at about 10 during the synthesis procedure. The products in the as-synthesized form and after calcination were characterized by means of XRD diffraction, nitrogen adsorption-desorption, and two different techniques of the solidstate 27A1 MAS NMR spectroscopy. Applying the cross-polarization (CP) magic angle spinning (MAS) spectroscopy makes it possible to determine the local environments of the aluminum species and to distinguish better between framework and non-framework aluminum.
06-P-18 - Control of formation of m e s o p o r o u s SBA-3 and SBA-1 through organic additives S. Che and T. Tatsumi
Division of Materials & chemical Engineering, Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan The synthesis and kinetics of formation of SBA-1 mesoporous molecular sieve was greatly affected by the addition of trimethylbenzene (TMB) isomers. The synthesis of SBA-1 was performed at 0~ using tetraethyl orthosilicate (TEOS) as the silicon source and cetyltriethylammonium bromide (CTEABr) as the template under acidic conditions. XRD shows that a well ordered hexagonal p6mm SBA-3 mesophase rapidly forms and then transforms to cubic Pm3n SBA-1 mesophase with proper TMB/CTEABr molar ratios. The presence of 1,2,3-TMB was the most favored to form p6mm hexagonal mesophase, and 1,2,4TMB showed an intermediate behavior.
06-P-19 - The influence of AI, La or Ce in the thermal and h y d r o t h e r m a l properties of M C M - 4 1 m e s o p o r o u s solids R.A.A. Melo and E.A. Urquieta-Gonzfilez*
Dep. Chem. Eng., C. Postal 676, S~o Carlos-SP, Brazil. e-mail." [email protected] The thermal (at 1153 K) and hydrothermal stability (at 933 K) of Si-, AI-, La- and Ce-MCM41 were studied. The solids were synthesized at 373 K. XRD data indicated that Si-MCM-41 presented the more resolved XRD pattern, therefore the most ordered porous structure. XRD and N2 sorption showed that the thermal treatment leads to a structure degradation with LaMCM41 showing the higher stability and Ce-MCM-41 suffering a total structure collapse. In the hydrothermal treatment, Ce-MCM-41 maintained above of 80% of its SBETarea and 55% of its primary mesoporous volume. In those thermally conditions La-MCM-41and A1-MCM41 were more stable than Si-MCM-41. The intensity of the band at 960 cm l in the FT-IR spectra can be well related with the order of porous array in the prepared MCM-41 solids.
203
06-P-20- Controlling the assembly of silica mesoporous materials by varying the decrease in pH J. Rathousk~, (a), J. t2ejka (a), P.J. Kooyman (b), M. Slabovfi (a) and A. Zukal (a)
a J. Heyrovskfi Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolej~kova 3, 182 23 Prague 8, Czech Republic, e-mail.'jiri.rathous~@/h-inst.cas.cz b National Centre for High Resolution Electron Microscopy, Delft University of Technology, Delft, The Netherlands, e-mail." [email protected] The synthesis of mesoporous silicas was performed from an isotropic reaction mixture using cationic surfactant as a structure directing agent. The decrease in pH, which causes the formation of solid particles, was achieved by hydrolysis of methyl acetate. The procedure enabled to obtain not only siliceous MCM-41 but also a less well-ordered hexagonal silica with extraordinary large surface area and silica with bimodal mesoporous structure containing the MCM-41 mesopore system and a system of mesopores with a mean diameter of 14 nm.
06-P-21 - Characterization of MCM-41 aged for different periods H. A1-Megren a ,T.-C. Xiao a, A.P.E York a, J. Sloan a, S. AI-Khowaiter b, S.-F. Ji a and M.L.H. Green a*
Wolfson Catalysis Centre, Inorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford, UK, OX1 3QR, email: [email protected] bPetroleum and Petrochemicals Research Institute, King Abdulaziz City for Science and Technology, P. O. Box 6086, Riyadh 11442, Saudi Arabia. A series of MCM-41 samples have been synthesised with varying aging times and characterized using XRD, TEM, N2-adsorption, Laser Raman and IR spectroscopy. The aging time effects the structure, crystallinity and adsorption properties of the MCM-41 molecular sieves. In our preparations, the sample aged for 7 d had the highest crystallinity, while an aging time over 7 d gives rise to irregular morphology of the MCM-41 particles, and a lower crystallinity. Calcination not only removes the template inside the molecular sieve, but also causes the sample to restructure and improves the crystallinity.
06-P-22 - Synthesis and characterization surfactant nanocomposites
of silica and aluminosilica-
E. Popovici a, A. Visan b, D. FilipC,G. Burtica d and R. Pode ~
"Al.I. Cuza" University of lasi, Romania, [email protected] b ICERP Ploiesti, Romania c"p.Poni" Institute of Macromolecular Chemistry, Iasi, Romania d "Politehnica" University of Timisoara, Romania Silica and aluminosilica-surfactant nanocomposite materials were prepared in the presence of [C18H37(CH3)3N]+ cations. The crystallinity, surface area, pore diameter distribution, thermal stability and the proportion of organic phase of these materials have been investigated in correlation with SiO2/R, AlzO3/R, SIO2/A1203 molar ratios of reaction mixture. It was found a specific interaction between organic cations and aluminum atoms of oxidic framework
204
06-P-23 - Improved thermal stability of mesoporous alumina support of catalysts for the isomerization of light paraffins V. Gonz~ilez-Pefia, C. M~irquez-Alvarez, E. Sastre and J. P~rez-Pariente
Instituto de Catdtlisis y Petroleoquimica (CSIC), Madrid, Spain. [email protected]
Mesoporous alumina samples have been synthesized using poly(ethylene oxide)-based nonionic surfactants. The effect that the addition of n-alkylamines to the synthesis gel has on the texture and thermal stability of mesoporous aluminas is studied. Textural and structural characterization using nitrogen adsorption, powder X-ray diffraction, 27A1nuclear magnetic resonance and Fourier Transform infrared spectroscopy, as well as catalytic n-hexane hydroisomerization tests are performed.
06-P-24 - Synthesis of mesoporous molecular sieves M C M - 4 8 under several reaction conditions S. Rodrigues da Rocha and L. Domiciano Fernandes
Universidade Federal Rural do Rio de Janeiro, e-mail. [email protected] Samples of MCM-48 mesoporous molecular sieves were synthesized by changing reaction conditions. Synthesis temperature was varied in the 373-423K range and crystallization time was 24-192 hours. Synthesis gel presented a molar composition of 1.0 SIO2:0.25 Na20:0.21.0 CTABr:60-400 H20. It was observed that highly ordered MCM-48 samples were obtained at 373K for 72 hours, from a gel presenting CTABr/SiO2 ratio of 0.55 and intermediate dilution. Samples recovered under this synthesis conditions had surface area greater than 1000 mVg, pore volumes of 0.8 cmVg and narrow pore size distribution. It was showed that MCM-48 was an intermediate phase between hexagonal and lamellar and that the transition to lamellar could be prevented by pH adjustment or NaCI addition.
06-P-25 - Parallel synthesis of mesostructured materials P. Behrens and C. Tintemann
Institut fiir Anorganische Chemic, Universitat Hannover, Callinstrafle 9, Hannover, Germany," Peter.Behrens@ mbox.acb, uni-hannover.de The formation of mesostructured materials of the M41S family and of related materials is a very complex field. Synthesis field diagrams (SFDs), which list the conditions of formation of different structural topologies as a function of the concentrations of the surfactant and silica precursors, reveal interesting details about the synthesis process. For the construction of an SFD, it is necessary to perform 120 to 150 synthesis experiments. The time necessary to construct an SFD for a certain set of reaction conditions (temperature, reaction time, basicity of the solution) can be reduced drastically by using the approach of parallel synthesis. Here we present an autoclave array allowing the parallel synthesis of 24 samples and our results obtained with this invention.
205
06-P-26 - Mesostructural transformation in the presence of fluoride anions Q.-H. Xia, K. Hidajat and S. Kawi*
Department of Chemical and Environmental Engineering, National University of Singapore, Singapore, Republic of Singapore - chekawis@nus, edu.sg Most mesoporous M41s materials are hydrothermally synthesized at temperatures below 150~ In some cases, there is a dependence of mesostructural transformation on time, temperature and compositions. When the temperature is over 150~ the formation of zeolites like ZSM-5 can take place. MCM-41 with enhanced hydrothermal stability can also be synthesized in fluoride medium. Here we report the factors influencing mesostructural transformation in fluoride medium. The appearance of lamellar and zeolite phases like ZSM-5 can be prevented through the molar compositions of precursor, and MCM-41 can be formed at temperatures as high as 170~ With the molar composition of 1.0 SIO2:0.54 NaOH: 0.50 CTMABr: 0.34 HF: 100 H20, the sequence of structural transformations does not undergo through the formation of lamellar and zeolites. We have also found that the mesostructure with type H2 hysteresis loop also possesses good hydrothermal stability.
0 6 - P - 2 7 - Swelled micelle-templated silicas (MTS): structure control and hydrophobic properties D. Desplantier-Giscard, A. Galameau, F. Di Renzo and F. Fajula
Laboratoire de Mat~riaux Catalytiques et Catalyse en Chimie Organique, UMR 5618 CNRSENSCM, Montpellier. France- [email protected] The synthesis of swelled-MTS with cylindrical mesopores is highly dependent on the nature of the swelling agent: aromatics allow to preserve the cylindrical geometry of pores, aliphatics change pore geometry to a system of interconnected spheres. This is due to the different sites of solubilization of the organics in CTAB micelles. For polarizable molecules, like aromatics, there are two sites of solubilization: near the micellar interface (interaction with ammonium head group) and in the micellar core. Aliphatic molecules are directly dissolved in the center of the micelles. Purely silliceous and aluminosilicates MTS with regular cylindrical pores up to 150 A were obtained. Uncalcined swelled MTS present an original property: they are hydrophobic and this will extend the applications of MTS as adsorbents.
06-P-28 - Synthesis of pure and iron-containing mesoporous silica. Effect of washing and removal of template on the porous structure L. Pasqua a, F. Testa a, R. Aiello a, F. Di Renzob and F. Fajula b
"Dip. Ingegneria Chimica e dei Materiali, Universit~t della Calabria, Rende, [email protected] bUMR 5618 CNRS, ENSCM, Montpellier, France. Synthesis of pure and iron-containing mesoporous silicas are carried out from CTMA mixtures containing different salts and hydrochloric acid. Ferric salts decrease the pH of the synthesis batch, except when complexed by fluoride ions. Samples obtained from neutral batches in the presence of fluoride are stable when washed and calcined. For syntheses at acidic pH and low temperature, a low degree of silica condensation is responsible for thin unstable silica walls. When surfactant molecules are extracted by washing or calcination, the porosity shrinks and disordered microporous solids are formed from ordered mesophases with 40 A micelles.
206 10 - Host-Guest Chemistry (Monday)
10-P-05- Non-acidic zinc zeolite systems: preparation methods, formation processes and catalytic properties in dehydrogenation of methanol N.Y. Usachev*, E.P. Belanova, A.V. Kazakov, V.P. Kalinin, A.S. Fomin, I.M. Krukovsky, G.V. Antoshin and O.K. Atal'yan; N.D. Zelinsky Institute of Organic Chemistry, RAS, 47
Leninsky Prosp., Moscow, Russia 117334, * FAX. (7095) 135-5328, e-mail: [email protected] New methods of micro heterogeneous super loaded ZnO/FAU systems synthesis were developed which allow to control oxide phases state. Their formation and properties were studied by TG-DTA, XRD and IR spectroscopy. High ZnO dispersion, which is provided by a decomposition of Zn salts on ion exchanged FAU, is favorable for catalytic conversion of CH3OH to water-free CH20 over these systems. Suggested methods can be used for a preparation of systems containing oxide phases of one or several transition metals which, due to their unusual properties, may find various applications in adsorption and catalysis.
10-P-06 - Incorporation of Ga ions into Y zeolites by reductive solid-state ion exchange R.M. Mih~lyi, H.K. Beyer and M. Keindl
Institute of Chemistry, Chemical Research Center, Hungary, [email protected] The incorporation of cationic Ga species into Y zeolites by reductive solid-state ion exchange and the oxidation state of introduced Ga were studied by IR spectroscopy and TPR. In mixtures of NH4Na-Y (Si/A1 = 2.5) with Ga203 thermally treated in a static H2 atmosphere, RSSIE and dehydroxylation, both consuming Br6nsted acid sites, were found to proceed simultaneously. The incomplete incorporation of cationic Ga was accompanied by release of part of the framework A1. In contrast, partially dealuminated Y zeolite (13.2) obtained by solid-state dealumination with (NH4)2[SiF6] could be completely exchanged by RSSIE, i.e. no de-hydroxylation occured due to higher thermal stability of the Br6nsted sites. Though reduction was found to be an indispensable step in the ion-exchange process in static H2, primarily formed Ga + ions seem to react immediately with the reaction product water to GaO + and H2.
10-P-07- Heavy metal exchanged zeolites as precursors for high temperature stable phases W. Schmidt and C. Weidenthaler
MPI fi~r Kohlenforschung, Mfilheim, [email protected], Germany Dense heavy metal containing phases were synthesized by the calcination of ion exchanged zeolites. The phases formed and their properties were dependent on various parameters such as ion exchange conditions, calcination conditions and composition of the zeolites. The type of exchanged cation determined the structures that were formed during the calcination. Generally, thermodynamically stable phases were formed at high temperature and sufficiently long calcination but by kinetic control metastable intermediates could be obtained as well. The control of these parameters enabled the synthesis of high temperature stable materials with well defined properties, which can be used as refractive materials and for catalysis or sensor technology.
207
10-P-08- Preparation and characterization of H-ZSM-5 exchanged with cobalt by solid state ion exchange M. Mhamdi l., S. Khaddar-Zinel'2, A. Ghorbel l, Y. Ben Taarit 3 and C. Naccache 3 ILaboratoire de Chimie des Matdriaux et Catalyse, Facultd des Sciences de Tunisi Tunisia. 2Institut Prdparatoire aux Etudes d'ingdnieur de Nabeul, El Merazka, Nabeul, Tunisia. 3Institut de Recherches sur la Catalyse Villeurbanne - France. Physico-chemical and catalytic properties of Co-ZSM-5 zeolites prepared by solid state exchange with different Co/A1 ratios and exchange temperatures were compared. The catalysts were characterized by XRD, Nz-BET, FTIR, UV-Vis and TPD of ammonia. Solidstate ion exchange generated new Lewis acid sites and one proton was exchanged per Co 2+ species. UV-Visible spectra indicate the presence of some minor cobalt oxides, not detected by XRD. Catalyst using Co/AI ratio equal to 1 and issued from exchange temperature equal to 500~ show high activity and selectivity towards acetonitrile by ammoxidation of ethylene.
10-P-09 - Cyclic chemical vapour deposition of TEOS on ZSM-5: effect of deposition temperature on shape selective performance H. Manstein, K.P. M~ller and C.T. O'Connor Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, South Africa - Heiko@chemeng. uct.ac.za H-ZSM-5 catalyst was modified with tetraethoxysilane using a cyclic chemical vapour deposition technique between 50~ and 400~ External activity was eliminated and the shape-selective performance of the catalyst could be improved to 90% para-isomer for all temperatures studied. Elevated deposition temperatures led to faster changes in the product distribution of xylenes but also to a more rapid decrease in the conversion of toluene which reduced the yield to the para-isomer. It was shown that modification at low temperatures resulted in the best improvements of the catalyst for the disproportionation of toluene.
208
11 - Post-synthesis Modification (Monday) I I - P - 0 6 - Dealumination of zeolite KL E.E. Knyazeva l, V.V. Yuschenko l, F. Fajula 2 and I.I. Ivanova l
1Laboratory of Kinetics and Catalysis, Department of Chemistry, Moscow State University, Moscow, Russia, e-mail: [email protected] 2Laboratoire de Mat6riaux Catalytiques et Catalyse en Chimie Organique, UMR 5618, Montpellier, France, e-mail:[email protected] Zeolite KL has been dealuminated by combining hydrothermal, ion exchange and acid attack treatments. The dealumination process is govemed by the removal of potassium ions from cationic sites located inside the cancrinite cages which exert a long-range inductive stabilization of the framework. Deep bed calcination of the partly exchanged samples promotes migration of these cations towards exchangeable sites. Further steam dealumination and acid attack allow to produce highly crystalline materials, with a global Si/AI ratio close to 10 and featuring strong acid sites 9
1 l - P - 0 7 - Formation of acidic hydroxyl groups during preparation of Pt/KL catalysts as studied by tH M A S N M R T. Sato (a), S.-I. Ito (a), K. Kunimori (a) and S. Hayashi (b) a Institute of Materials Science, University of Tsukuba, Tsukuba, Japan b National Institute of Materials and Chemical Research, [email protected], Japan Acidic hydroxyl groups in Pt/KL zeolite prepared by the ion exchange method have been characterized quantitatively by IH MAS NMR. After the ion exchange by [Pt(NH3)4] 2+, the calcination process produces acidic hydroxyl groups. NH4 + ions produced by decomposition of [Pt(NH3)4] 2§ are considered to be the origin 9 The H2 reduction process also produces the 9 9 9 acidic hydroxyl groups by the reaction Pt 2 + + H2 ---> Pt 0 + 2H + . This9 indicates that after the calcination P(+ ions are dominant species. ~H chemical shift depends on the concentrations of Pt and the acidic hydroxyl groups and also on the Pt state. The stronger acidity is originated in the following order of Pt 2§ > H § > K §
II-P-08 - Synthesis and characterization of mesopore Y zeolite B.
Ma
a,b, W.F. Sun c, Z.L. Sun b and L.R. Chen a
aLanzhou Institute of Chemical Physics, The Chinese Academy of Sciences, Lanzhou, P. R. China," bFushun Petroleum Institute, Fushun, P R China CFushun Research Institute of Petroleum and Petrochemicals, Fushun, P R China In this presentation, the HY zeolite with a lot of secondary pores (the diameters of the secondary pores are larger than 2 nm), unblocked channels and low acid site density has been prepared by steaming and acid leaching treatment of HY zeolite. The steaming and acid leaching treatment conditions were examined in details, and the optimal treatment conditions were determined. This kind of HY zeolite, so called mesopore HY zeolite, showed higher activity than HY zeolite in hydrocracking larger molecules 9
209
1 l-P-09 - Controlling the pore size of HI~ zeolite by improved chemical vapor deposition of (CH3)aSi-O-Si(CHa)a Y. Chun a*, X. Ye b, Q.H. Xu a and A.-Z. Yan a
Department of Chemistry, Nanjing University, Nanjing 210093, China,"[email protected] bDepartment of French, Nanjing University, Nanjing 210093, China The pore size of large-pore zeolite HB is controlled by an improved chemical vapor deposition (CVD). In this method, ammonia or tripropylamine was used to protect the acidic sites in zeolite before deposition of (CH3)3Si-O-Si(CH3)3, differently from the conventional CVD. The pore volume of zeolite HI3 was reduced and the pore size was narrowed upon this modification. The results from IR spectra and catalytic decomposition of isopropanol demonstrated that the modified samples showed stronger acidity than that prepared from conventional CVD. In the transformation of trimethylbenzenes (TMB), conversion of 1,3,5TMB was suppressed while conversion of 1,2,3-TMB was almost unaffected on the improved CVD samples; the selectivity of 1,2,4-TMB on these samples was increased in the alkylation reaction of m-xylene with methanol.
I I - P - 1 0 - I n f l u e n c e of pH of the solution on r e a l u m i n a t i o n of B E A zeolite Y. Oumi (a), R. Mizuno (a), K. Azuma (a), S. Sumiya (a), S. Nawata (b), T. Fukushima (b), T. Uozumi (a) and T. Sano (b)
a School of Materials Science, Japan Advanced Institute of Science and Technology, Tatsunokuchi, Ishikawa 923-1292, [email protected], Japan. b Tosoh Corporation, Shin-nanyo, Yamaguchi 746-8501, Japan. The influence of pH value in the solution on the realumination process of BEA zeolite was investigated by mean of nitrogen adsorption, XRD, 27A1 MAS NMR and FT-IR. It was found that non-framework aluminum species (octahedrally coordinated aluminums) in the solution are easily reinserted into the framework of dealuminated BEA zeolite by controlling the pH value o( the solution below 7. The cumene cracking activity of the realuminated BEA zeolite at pH 5.1 was comparable to that of the parent BEA zeolite. The influence of aluminum species in the solution on the realumination process was also investigated using various aluminum compounds.
I I - P - I I - Formation of carbon-intercalated molybdenum sulfides J.-S. Chen,* Y. Wang, Y. Guo, Y. Zou and W. Xu
Key Laboratory of Inorganic Synthesis and Preparative Chemistry Jilin University. [email protected], Changchun, P R. China Molybdenum sulfide compounds (MoS2-C) with intercalated carbonaceous matter have been obtained by pyrolysis of a surfactant-containing mesolamellar molybdenum sulfide in a nitrogen flow at various temperatures. The samples contain about 22 wt% of carbon, and the interlayer distance for the MoS2-C compounds is about 9.8 A. The solid obtained by treatment at 973 K exhibits considerable N2 adsorption capacity. The electrical conductivity for the MoS2-C materials is higher than that of the pristine MoS2 at low measurement temperatures, and it strongly depends on the pyrolysis temperature. It is believed that the carbon intercalated between the MoSa sheets plays a role in the conductivity enhancement.
210
1 I - P - 1 2 - Characterization of partly-detemplated GaPO4-LTA S.-F. Yu, C.-Y. Xi, H.-M. Yuan and J.-S. Chen*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, [email protected], edu. cn, Changchun, P. R. China Gallophosphate GaPO4-LTA crystals were heated under vacuum and in a nitrogen atmosphere, respectively. It has been found that the resulting materials are partly-detemplated and retain the LTA framework structure even in moist atmosphere. The thermally-treated GaPO4-LTA compounds exhibit considerable adsorption capacities for water and nitrogen but the adsorption behavior depends on the pyrolysis conditions. In contrast to the channels of AFI in which the generation of carbon nanotubes has been realized, the a-cages of GaPO4LTA have a space large enough for the formation of fullerene-like materials that might exist in the carbonaceous matter of the partly-detemplated GaPO4-LTA compound.
l l - P - 1 3 - Another study on the microwave heating of zeolite without special loading materials J. Dong (a), L. Xie(a), X. Jing(a), H. Xu (a), F. Wu (b) and J. Hao (c)
a Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi, P.R.China* email: jxdong @ public ty.sx.cn; b Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P.R.China; c Department of Information Engineering, Taiyuan University of Technology, Taiyuan 030024, PR. China The heating and phase-transformation of zeolites caused by microwave irradiation at 2450MHz without special loading materials are examined. It is found that zeolite X was heated to 1473K about 90 seconds at power output of 400W. It is verified that the center of microwave absorption is not water or surface hydroxyl groups, not silica in zeolites, but electron bearing AIO4 tetraedra. The ability of zeolites to absorb microwave energy depends on zeolitic framework structure, exchangeable cations, Si/AI molar ratio, as well as adsorbed compounds in zeolite.
II-P-14 - Microwave plasma treatment as an effective technique for activation of zeolite catalysts I.I. Lishchiner (a), O.V. Malova (a) and E.G. Krasheninnikov (b)
(a) Institute of Organic Chemistry RAS, [email protected] (b) Russian Research Center "Kurchatov Institute" Moscow, Russia An afterglow microwave plasma with stabilized pulse power was applied to the activation of zeolite catalysts for isobutane alkylation with butenes. It was found that the pretreatment of zeolite catalysts in a microwave plasma discharge affected their properties. The catalysts exhibited higher activity, stability in operation, and selectivity (the fraction of trimethylpentanes in the alkylate increased). The properties of catalysts after plasma activation depend on the treatment conditions such as plasma "temperature" and nonequilibrium character and depend only slightly on the initial activity of catalysts, which is primarily controlled by the catalyst preparation conditions.
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1 I - P - 1 5 - Synthesis and characterization of microporous titanium-silicate materials S. Mintova, B. Stein, J.M. Reder and T. Bein*
Department of Chemistry, University of Munich, Butenandtstr. 11-13 (E), 813 77 Munich, Germany, svetlana, mintova@cup, uni-muenchen, de The synthetic counterparts of the minerals zorite and pharmacosiderite were hydrothermally synthesized in SiQ-TiOz-MzO-(TMA)20-water systems using atypical precursor gel compositions which result in different crystal morphologies. Nanocrystalline pharmacosiderite with individual particles of <100 nm were prepared using an organic template. Micrometer sized ETS-4 with a flattened cuboid morphology was also synthesized. The ionexchange of Na + and K + for NH4+, Sr2+ and Mg 2+ was performed. The as-synthesized and the ion-exchanged samples were characterized by XRD, SEM, as well as IR, UV-vis and Raman spectroscopies.
1 I-P-16 - From borosilicate to gallo- and aluminosilicate zeolites: new methods for lattice substitution via post-synthetic treatment C.Y. Chen and S.I. Zones
Chevron Research and Technology Co., Richmond, CA 94802, USA, [email protected] In this paper we report new methods for the lattice substitution of heteroatoms in large and extra-large pore borosilicate zeolites via post-synthetic treatment to prepare catalytically more active zeolites. Ga-SSZ-33, A1-SSZ-33 and AI-UTD-1 prepared from B-SSZ-33 and B-UTD1, respectively, are discussed as examples. The materials are characterized with various physicochemical techniques and catalytic reactions. In particular, the advance of these methods is demonstrated by the exceptionally high activity of the resulting A1-SSZ-33 for acid-catalyzed hydrocarbon conversions.
I I - P - 1 7 - Studies on the structure of zeolite Y modified by radio-frequency fluorocarbon plasma treatment S. Yamazaki a, T. Nishimura a, K. Furukawa b, H. Ijiri c and K. Tsutsumi d
a Shizuoka Institute of Science and Technology, Shizuoka, Japan, [email protected] b Adv. Sci. and Tech. Center for Cooperative Research, Kyushu University, Fukuoka, Japan c Interdisciplinary Graduate School of Eng. Sci., Kyushu University, Fukuoka Japan d Toyohashi University of Technology, Toyohashi, Japan H-type zeolites Y with silica/alumina ratios of 5.6 and 29 were modified by a radio frequency CF4 plasma treatment. On the basis of the weight loss due to the elimination of carbon and fluorine atoms observed by TG/DTA-MASS spectroscopy, functional groups existing on the surface were stable up to 700K. The amount of component elimination in high aluminum content zeolite Y was larger than that in low aluminum content, which suggests that the functional groups were introduced near aluminum site in the framework.
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I I-P-18 zeolites
- Dual-temperature
reagent-less
ion-exchange
separations
on
V.D. Timofeevskaja, O.T. Gavlina, V.A. Ivanov and V.I. Gorshkov Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119899, Russia E-mail." ivanov@physch, chem. msu.su Dual-temperature ion-exchange purification of concentrated solutions of alkali metal salts from divalent and monovalent ion admixtures on a number of natural and artificial zeolites without auxiliary reagents consumption is studied. Two types of dual-temperature techniques - the temperature-swing mode of separation and the parametric pumping - are used.
I I - P - 1 9 - Rare earth exchange in small pore zeolites and its effect on their hydrothermal stability G. Cao, M.J. Shah and W.A. Wachter ExxonMobil Research and Engineering Company, [email protected], USA While zeolites with 8-ring pore openings have been the target of numerous studies of ionexchange because of their relevance to water softening and radioactivity management, study of their rare earth ion-exchange properties in the context of catalysis has been scarce. We report here solution and solid-state rare earth exchange reaction in ZK-5 and chabazite, the kinetics and thermodynamics of the solution exchange, and the effect of exchange on the hydrothermal stability of the zeolites. While the solid-state exchange method results in loss of crystallinity, the solution exchange method is effective, but the exchange rate is slow even at elevated temperatures. The exchange isotherms show that selectivity for rare earth cation is low with both zeolites. Rare earth exchange is found to improve the hydrothermal stability of both zeolites, for which a speculative explanation is forwarded.
1 l-P-20 - Modification of mordenite and natural clinoptilolite by copper: role of drying temperature I. Rodriguez-Iznaga (a, b), V. Petranovskii (r G. Rodriguez-Fuentes (b), N. Bogdanchikova (c) and M. Avalos (c) a Higher Mining-Metallurgical Institute ofMoa, Las Coloradas, 83329 Moa, Holguin, Cuba b Zeolites Engineering Laboratory, Institute of Materials and Reagents (IMRE), Faculty of Physics, University of Havana, 10400 Havana, Cuba c Centro de Ciencias de la Materia Condensada, UNAM, Ensenada, Mexico, [email protected] The influence of pre-reduction heating treatment in air on the reducibility of copper supported on clinoptilolite and mordenite was investigated. After dehydration the process of Cu-mordenite reduction is hindered and the formation of copper particles is suppressed. This result could be used for the stabilization of Cu inside the zeolite pores and the prevention of copper agglomeration on the external surface, which could lead to improved catalysts for de-NOx processes.
213
II-P-21 - Study on the acidity of modified H Y zeolites prepared by combination of chemical dealumination and h y d r o t h e r m a l treatment M. Han, L.-P. Zhou, X.-W. Li and L.-Q. She* College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, liqin@chemms, chem.pku, edu. cn, China Acidity of modified HY zeolites prepared by combination of chemical dealumination and hydrothermal treatment have been characterized by IR, MAS NMR and n-butylamine titration. The results showed that by increasing the level of dealumination, the total amount of acid sites decreased while the strongest acid sites (H0 < -8.2) increased. The strength population profile of acid sites revealed that only the aluminum atoms associated with the stronger acid sites (-8.2 < H0 < -5.6) were extracted from the framework during the dealumination steps. These results were correlated with the population of Si(nA1) groupings obtained from the spectra of 29Si MAS NMR. The acidity changes at each step of preparation procedure are discussed.
11-P-22 - Modification of Beta-zeolite by dealumination and realumination J.Y. Zhang, L.-P. Zhou and X.-W. Li
Department of Chemistry, Peking University, Beijing 100871, China xwli@chemms, chem.pku, edu. cn The dealumination and realumination of low sodium [3-zeolite have been studied by IR spectroscopy and powder X-Ray diffraction. The calcination-dealuminated HI3 was easily realuminated by direct treatment with aluminate sodium solution. After transformation into protonic HI3, the framework Bronsted sites (IR band at 3610 cm ~) were restored and the acidity was the same as in the original HI3. The realumination of acid dealuminated HI3 was difficult, but could be achieved with aluminate sodium solution by hydrothermal treatment in autoclave. This incorporation of A1 into zeolite framework increased the number of acid sites, in particular that of weak acid sites which in comparison with parent HI3.
11-P-23 - Ultrastable zeolites Y (USY) modified with p h o s p h o r u s and boron A.V. Abramova a, Y.V. Slivinsky a, L.Y. Kitaev b, A.A. Kubasov b, H. Lechert c, W.D. Basler c, V.V. Yushchenko b and Z.M. Matieva a
a A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky prospect, 29, 117912, Moscow, B-71, Russia, e-mail." [email protected] b Moscow 34. V. Lomonosov State University, Moscow, Russia r Institute of Physical Chemistry, University of Hamburg, Hamburg, Germany USY zeolite has been modified by an acid treatment with H3PO4 and H3BO3. The properties of the modified samples have been investigated by various methods. After loading with platinum the catalytic properties with respect to n-hexane isomerisation have been studied. The modification changes significantly the adsorption properties. The modified catalysts are more active in n-hexane isomerization than USY.
214
11-P-24 - Structural properties and sieving effects of surface modified ZSM-5 S. Zheng l, H. Heydenrych l, H.P. R~ger 2, A. Jentys I and J.A. Lercher l l TU-Mfmchen, Institute f Chemical Technology, Garching, Germany, http.'//www, chemie, tu-muenchen, de/tc2/ ; 2Sud-Chemie A G, Bruckmuehl-Heufeld, Germany Chemical liquid deposition of tetra-ethoxysilane was used to modify the external surface and pore mouth region of HZSM-5 with different crystal sizes. After modification, a decrease in the overall concentration of silanol and bridging hydroxide groups was observed. Modification led to only minor changes in the micropore volume of HZSM-5 and in the diffusivities of toluene and p-xylene, while the diffusivity of o-xylene was substantially suppressed and the p-selectivity in the disproportionation of toluene was significantly increased. A more significant modification effect could be achieved with a single cycle silanization of large HZSM-5 crystals compared to a three-cycle silanization of small crystals.
11-P-25 - The use of binary adsorption studies to investigate the effect of h y d r o t h e r m a l treatment on zeolites Rho and M o r d e n i t e L.H. Callanan (a), C.T. O'Connor (b) and E. van Steen (b) a Lehrstuhl II fur Technische Chemic, Tech. Uni. M~nchen, [email protected], Germany," b Catalysis Research Unit, Dept. of Chem. Eng., University of Cape Town, South Africa Adsorption studies of methanol, water and ammonia, and binary mixtures of these compounds, have been used to explain the difference in the change in reaction behaviour of zeolites Rho and mordenite in the methanol amination reaction after hydrothermal treatment. It is found that the changes in the total adsorption capacities were related to the changing pore volumes and to the presence of extra-framework aluminium within the pores of the catalysts. The changes in the reaction performance of the catalysts for the methanol amination reaction were also correlated to the changes in acidity, structure and adsorption capacity of the catalysts.
11-P-26 - Acid sites in thermal transformations of Ca-rich clinoptilolite G.P. Valueva a, I.S. Afanassiev b, E.A. Paukshtis c, Y.V. Seryotkin a, N.K. Moroz b and A.A. Budneva ~
~Institute of Mineralogy and Petrography, Acad. Koptyug ave. 3, 630090, Novosibirsk, Russia bInstitute of Inorganic Chemistry, Lavrentyev ave, 3, 630090, Novosibirsk, Russia CInstitute of Catalysis, Lavrentyev ave, 5, 630090, Novosibirsk, Russia Five cycles of heating (450 ~ exerted over a Ca-rich clinoptilolite from basalt, resulted in the distortion of structure and its stabilization. The symmetry was lowered from monoclinic to triclinic, positions of extraframework cations and H20 molecules were retained. These changes conform with the formation of framework (bridging) OH groups, detected by IRand NMR-spectroscopy. The most drastic changes occurred during the first heating, exhibited as deficiency of rehydration and the most extensive OH group formation. During further cycles OH groups changed their positions and the deficiency of rehydration stabilized.
215
11-P-27- The effect of calcination on the isomorphously substituted microporous materials using ozone D. Mehn a, A. Kukovecz a, I. Kiricsi a, F. Testa b, E. Nigro b, R. Aiello b, G. Daelen c, P. Lentz c, A. Fonseca c and J. B.Nagy c
aApplied Chemistry Department, University of Szeged, H-6720 Szeged, Hungary bOip. di Ingegneria Chimica e dei Materiali, Univ. della Calabria, 1-87030 Rende (CS) Italy r de RMN, Facult6s Universitaires Notre-Dame de la Paix, 61 Rue de Bruxelles, 5000 Namur, Belgium The templating organic molecules or ions have been eliminated by using an oxygen or an ozone treatment. The mild conditions used for the latter preserve quasi intact the various tetrahedral framework elements in B-, Co-, Co, A1-ZSM-5 and in Ga-MCM-22 zeolites.
11-P-28- Aiumination of siliceous zeolites A. Omegna, M. Haouas, G. Pirngruber and R. Prins
Lab. Tech. Chem., ETH-Z~irich, CH-8092 Ziirich, Switzerland (prins@tech. chem. ethz. ch) The post-synthesis incorporation of aluminium into the lattice of pure siliceous zeolite-~ was attempted using aluminium isopropoxide as aluminating agent in a non-aqueous environment. The XRD structural analysis of the Al-grafted materials showed an increase in the unit cell parameters which was associated with the insertion of aluminium into the framework. Quantitative multinuclear NMR investigation showed that the amount of framework aluminium incorporated into the zeolite lattice was related to the concentration of defect sites in the parent Si-[3 zeolite. This indicated that the alumination proceeds through a mechanism which involves the reaction between AI(OPr)3 and silanol groups at defect sites. Calcination after alumination led to the completion of the process, whereby octahedral-coordinated aluminium, (partially) attached to the framework, was transformed into tetrahedralcoordinated framework aluminium.
11-P-29- New hydrophobic Ti-Beta catalyst obtained by silylation and its catalytic performance for olefin epoxidation A. Corma, M.E. D6mine, J.A. Gaona, M.T. Navarro, F. Rey* and S. Valencia.
Instituto de Tecnologia Quimica (UP V-CSIC), Valencia, Spain. frey@itq, upv. es. Silylated Ti-Beta materials show a superior selectivity for epoxidation reactions than analogous fluoride synthesized Ti-Beta. This enhanced yield to the desired epoxide was attributed to the synergetic effect of the basic amine adsorbed on the Ti sites and the presence of silyl groups anchored on the silanol and/or titanol groups of the precursor Ti-Beta catalyst which prevents the oxirane ring opening reaction.
216
I I - P - 3 0 - M F I zeolite with u n i f o r m m e s o p o r e s created by alkali t r e a t m e n t M. Ogura, E. Kikuchi and M. Matsukata
Department of Applied Chemistry, Waseda University, [email protected], Japan. Mesopores were created in MFI zeolite by alkali treatment technique without deterioration of zeolitic microporous structure. The size of formed mesopore is ca. 4 nm and more uniform than that of MCM-41. Mesopores are formed along a boundary of MFI crystallite twinning, which shows a weak quality against alkalinity, apart from the microporous structures. This unique structure causes superiority in acid catalysis because of the combination of its strong acidity originated by ZSM-5 with newly created mesoporosity.
217 12 - In-situ Spectroscopy and Catalysis (Monday) 1 2 - P - 0 5 - Study of relationship between mordenite acidity and structure with calcination temperature Z. Zhu, Q. Chen and W. Chen
Shanghai Research Institute of Petrochemical Technology, China, [email protected] The nonstructural aluminum, removed from H-MOR framework during calcination, is located within zeolite pores in octahedral and pentacoordinated aluminum oxides, and does not affect the acidity of Br0nsted acid sites remaining in the framework. Although H-MOR dealumination amounts to about 60% of the previous framework aluminum during calcination at 1123 K, its crystallinity is still over 70%, with its adsorption capacity decreasing to 56% of the previous. In addition to framework dealumination, the dehydroxylation of H-MOR framework is another important factor resulting in both decrease of Br6nsted acid sites and increase of Lewis acid sites during calcination at a temperature higher than 923 K.
12-P-06 - Infrared observation of the stable carbenium ions formed by adsorption of olefins on zeolite Y at low temperatures S. Yang, J.N. Kondo and K. Domen
Chemical Resources Laboratory, TITech, Yokohama, Japan. E-mail. kdomen@res, titech, ac.jp. The formation of alkenyl carbenium ions, characterized by an IR band at ca. 1510 cm "1, was successfully observed by adsorption of 1-methylcyclopentene, methylenecyclopentane and 1methylcyclopentanol on zeolite Y. At temperatures as low as 150 K, the carbenium ions were formed soon after introducing the olefins. The characteristic band at ca. 1510 cm 1 increases in intensity with the elevation of temperature and is stable up to 373 K. For MCPOH, the characteristic band appears at temperatures above 245 K after its dehydration. The formed species were assigned to be dimerized alkenyl carbenium ions by calibrating the acid sites of HY using 1-butene at 235 K. UV-vis spectroscopic studies confirm the formation of momoenylic and dienylic carbenium ions, with bands at 323 and 400 nm, respectively.
12-P-07 - Characterization of aluminosilicate zeolites by UV-Raman spectroscopy Y. Yu (a), G. Xiong (b), C. Li (b), and F.-S. Xiao (a*)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry & Department of Chemistry, Jilin University, Changchun 130023, [email protected], China. b State Key Laboratory of Catalysis, Dalian Institute of Chemistry Physics, Chinese Academy of Sciences, P. O. Box 11 O, Dalian 116023, China. A series of aluminosilicate zeolites are characterized by UV Raman spectroscopy for the first time. UV-Raman spectra of various zeolites give strong and clear bands with high resolution, while conventional Raman spectra of these zeolites are difficult to obtain because of a strong background fluorescence. A summary of these UV Raman spectra over various aluminosilicate zeolites suggests that the bands at 470-530, 370-430, 290-410, and 220-280 cm l are assigned to the bending modes of 4-, 5-, 6-, and 8-membered rings of aluminosilicate zeolites, respectively.
218
12-P-08 - Adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on sodium-ion exchanged faujasites with different Si/A! ratios I.A. Beta (a), H. BOhlig (a), J. D6bler (b), H. Jobic (c), E. Geidel (b) and B. Hunger (a)
a Wilhelm-Ostwald-Institutfiir Physikalische und Theoretische Chemie, Universitgit Leipzig, D-04103 Leipzig, Germany, [email protected] b Institutf~r Physikalische Chemic, Universitcit Hamburg, D-20146 Hamburg, Germany c CNRS, Institut de Recherches sur la Catalyse, F-69626 Villeurbanne Cedex, France The adsorption of furan, 2,5-dihydrofuran and tetrahydrofuran on sodium-ion exchanged faujasites with different Si/A1 ratios was studied by combining temperature-programmed desorpt!on (TPD), inelastic neutron scattering (INS), Fourier transform infrared spectroscopy (FTIR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), quantum mechanical computations and Monte-Carlo simulations.
12-P-09- DRIFT and FTIR spectra of N2 and C2H4 adsorbed on CuNaY G. H~ibner and E. Roduner
Universit~t Stuttgart, Germany e.roduner@ipc, uni-stuttgart, de DRIFT and FTIR spectra of N2 and C2H4 adsorbed on vacuum dehydrated CuNaY were measured. Due to the anisotropic environment the symmetry of these probe molecules is broken and both the N2 stretching mode and the al modes of CzH4 are active. N2 interacts with sites like Na + and Cu(I) as shown by absorption bands at 2335 cm l and 2299 cm -1, respectively. At higher loadings an interaction with acidic OH groups takes place, as confirmed by the simultaneous decrease of the OH band at 3645 cm ! and the growth of a shoulder around 2327 cm "l. The spectra of C2H4 show two strongly redshifted band pairs of the al modes at 1545 cm l and 1535 cm i and at 1278 cm ~ and 1264 cm "l, respectively, proving the existence of two different Cu(I) sites. The interaction of C2H4 with Cu(l) sites is confirmed by coadsorption of N2 which cannot displace C2H4 from their adsorption sites.
12-P-10 - Raman study of the building units in the zeolite structure P.P.H.J.M. Knops-Gerrits (a)*, X.-Y. Li (b), N.-T. Yu(b) and P.A. Jacobs(c)
(a)Ddpartement de Chimie, Universitd Catholique de Louvain (UCL), Belgium (b) Chemistry Department, HKUST, Hong-Kong; (c) COK, KU Leuven, Belgium, * Corresponding Author. Tdl ." (32)10-47 29 39 Fax : 47 23 30; [email protected] In the development of zeolite science, infrared spectroscopy has been one of the major tools for structure and reactivity characterization. However, the field of zeolite Raman spectroscopy is gaining importance. The Raman effect is an intrinsically weak phenomenon, and Raman spectra of zeolites are often obscured by a broad fluorescence. Just like IR spectroscopy, Raman can detect small, X-ray amorphous zeolite particles. Therefore, Raman spectroscopy has been used to examine zeolite synthesis mixtures with ex-situ methods (with separation of solid and liquid) and in-situ methods. In this work we give an overview of the zeolite framework vibrations, zeolite synthesis, adsorption on zeolites and metal substitution and ion exchange in zeolites.
219
12-P-11 - Positron annihilation study in M C M - 4 1 H.Y. Zhang !'2, Y.J. He Z'2, Y.B. Chen l, H.Y. Wang 1'2 and T. Horiuchi 3 1
.
.
.
.
.
.
Department of Physws, Tslnghua Umverstty, Betjing 100084, P. R. China Key laboratory for Quantum Informatton and Measurements, MOE, P. R. China," 3National Industrial Research Institute of Nagoya, Hirate-cho, Kita-ku, Nagoya 462-8510, Japan 2
Positron annihilation lifetime spectra of MCM-41 and zeolite Y were measured in vacuum and air. For MCM-41 a very long positron lifetime component could be observed not only in vacuum, but also in air, while for zeolite Y it can only be observed in vacuum with a weak intensity. These peculiar positron annihilation characteristics were explained by air quenching mechanism of o-Ps annihilation in MCM-41. For comparison, positron annihilation lifetime spectra of MCM-41 were also measured in different O2 and N2 level. The results show that oxygen is more effective in quenching than nitrogen because of its spin unpaired electron.
12-P-12 - N M R studies on the pyrrole adsorption exchanged zeolites of type FAU
over Na +, Li +
M. Sfinchez-Sfinchez and T. Blasco*
Instituto de Tecnologia Quimica (UPV-CSIC), Universidad Polit6cnica, Avda. de los Naranjos s/n, 46022-Valencia, Spain. E-mail: [email protected] Multinuclear solid state nuclear magnetic resonance (NMR) has been applied to study the interaction of pyrrole with extra framework compensating cations in zeolites LiNaY and LiNaX. Upon adsorption over zeolite LiNaY, Na + and Li + cations migrate towards accessible positions in the supercage to interact with one molecule of pyrrole. The adsorption over zeolite LiNaX decreases the mobility of SIII' Na + cations, while pyrrole molecules do not interact with Li + cations. At lower loading, pyrrole adsorbs over more basic sites, which are associated with Na + cations in zeolite LiNaY.
12-P-13 - V a r i a b l e - t e m p e r a t u r e F T I R study of the equilibrium between Cbonded and O - b o n d e d carbon m o n o x i d e in H - Z S M - 5 G. Turnes Palomino (a), M. Pefiarroya Mentruit (a), A.A. Tsyganenko (b), E. Escalona Platero (a) and C. Otero Arefin (a)
a Dpto. de Qu[mica, UIB, 07071 Palma de Mallorca, Spain b Institute of Physics, St. Petersburg State University, 198904 St. Petersburg, Russia Infrared spectroscopic studies have shown that adsorbed carbon monoxide interacts with Bronsted acid Si(OH)A1 groups of the zeolite H-ZSM-5 forming hydrogen-bonded H'"CO and H'"OC species, which are characterized by C-O stretching IR absorption bands at 2175 and 2112 cm l , respectively. By means of variable-temperature FTIR spectroscopy, these Cbonded and O-bonded adducts were found to be in a temperature dependent equilibrium which can be described as ZH-..CO-~---- ZH."OC, where Z stands for the zeolite framework. The corresponding enthalpy change was found to be AH~ = 4.2 kJ mol 1, as derived from a van't Hoff analysis of the intensity of the corresponding IR absorption bands as a function of temperature.
220
12-P-14 - Role of the various acid sites in M O R on o-xylene conversion: an in-situ I.R a p p r o a c h O. Marie (a), F. Thibault-Starzyk* (a), P. Massiani (b) and J.C. Lavalley (a)
a Laboratoire Catalyse & Spectrochimie, CNRS ISMRA, Caen, [email protected], Laboratoire de R~activit~ de Surface, CNRS-UPMC, Paris, France
France b
Two different bridged OH are distinguished in MOR (in side pockets or main channels). The activity of these two different acid sites was studied by in situ IR spectroscopy of working catalysts. Progressive Na + / H + exchange was used to prepare the various samples. Acid strength in the main channels is not influenced by the presence of Na + in the side pockets. In xylene isomerisation, OH groups in the side pockets strongly influence initial selectivity for disproportionation and final coke amount, although we show that they do not directly participate in the reactions.
12-P-15 - F T I R - Studies on adsorption and d e c o m p o s i t i o n of N O on in-situ synthesized ZSM-5/cordierite catalysts N. Guan *a, X. Shan a, X. Zeng a, S. Xiang a, A. Trunschke b and M. Baerns b
Department of Chemistry, Nankai University, 300071 Tianjin PR. China blnstitute of Applied Chemistry, Rudower Chaussee 5, Berlin-Adlershof , D-12489 Berlin, Germany The adsorption of NO on in-situ synthesized CuZSM-5/cordierite monolithic catalysts of different Si/A1 ratios was studied by diffuse reflectance FTIR spectroscopy at different NO partial pressures from 500 ppm to 2000 ppm and temperatures from 298 K to 773 K. At room temperature, Cu mostly exists in oxidized Cu 2+ form. A lot of N20 species were observed on the surface even at room temperature. A band at 2133 cm l is attributed to NO+-Oiattice and only related to the number of lattice A1 in the zeolite. There may exist a copper-zeolitesubstrate interaction on such as synthesized monolithic catalysts.
1 2 - P - 1 6 - Acid sites in dealuminated mordenite V.L. Zholobenko and G.P. Mitchell
Keele University, Staffordshire, UK (fax:44 1782 584352; e-mail: [email protected]) TGA, TPD-MS and FTIR characterisation of acid sites in dealuminated mordenite has been carried out for quantitative determination of the number of Bronsted acid sites and their accessibility using ammonia, pyridine, mono- and diamines as probe molecules. The uniform decrease in intensity of the HF and LF OH bands of the bridging hydroxyls observed in the dealuminated materials can be explained by the similar degree of dealumination in the 8- and 12-ring channels of the zeolite structure or by its partial reconstruction during the sample activation. Our data suggest that mild dealumination of the mordenite framework provides more uniform conditions for transport and adsorption in the 8- and 12-ring channels, representing the first step towards formation of the three-dimensional dealuminated mordenite catalysts.
221
12-P-17- Infrared study of iron-exchanged Y Zeolite and its HDS activity M. Nagai, O. Uchino and S. Omi
Graduate School of Bio-applications and Systems Engineering, Tokyo University of Agriculture and Technology, Nakamachi, Koganei, Tokyo, Japan. The acid sites of iron-exchanged Y zeolite were studied using NH3-TPD and diffuse reflectance FTIR spectroscopy. The Bronsted acids of three iron-exchanged Y zeolites were correlated with the activity for dibenzothiophene HDS at 240 and 280~ and 10.1 MPa. The FTIR data on NH3 and NO adsorption showed that Fe 2§ ions on the zeolites was correlated with their activities during dibenzothiophene HDS.
222
1 7 - Principles of Adsorption (Monday) 17-P-05 - Confinement in model host materials: experimental study of quasi-(1D) systems J.P. Coulomb a, N. Floquet a, C. Martin b, Y. Grillet c and J. Patarin d
aC.R.M.C2 - CNRS, Campus de Luminy, Marseill, France; bL.P.I.I.M. - URA 773, Campus de St. J6rome, Marseille, France," cC. T.M.- C.N.R.S, Marseille, France, aLab. des Mat6riaux Min6raux, Universit6 de Haute Alsace, Mulhouse, France. We present a summary of our most recent experimental results concerning the properties of confined quasi-(1D) molecular systems both at the macroscopic scale (thermodynamic) and microscopic scale (structure and dynamic). In the mesoscopic size regime (2 < O MCM-4~< 4 nm) the confined matter undergoes phase transitions as bulk matter. But the transition temperatures are strongly displaced towards the low temperature side. In the microscopic size regime (0 AIPO4-5--< 1 nm) the intrinsic phase transitions of confined matter vanish.
17-P-06 - Studies on desorption behavior of organics on siliceous ferrierite B. Qian, Y. Zeng and Y.-C. Long*
Department of Chemistry, Fudan University, Shanghai 200433, P. R. of China yclong@)Cudan.edu.cn. FAX." (+86)-21-5653-3195 TG/DTG/DTA was employed to determined the Aw value, affinity index, for comparing the interaction between the perfect Si-O framework of siliceous ferrierite and the adsorbed organic compounds with various functional groups, such as alkyl-amines, alkyl-alcohols and n-alkanes. The relation between Av values and interaction strength (AH0 is discussed as well.
17-P-07 - Investigation of hydrocarbon adsorption on large and extra-large pore zeolites C.Y. Chen and S.I. Zones
Chevron Research and Technology Co., Richmond, CA 94802, USA, [email protected] Large and extra-large pore zeolites with one-dimensional channel systems (SSZ-24, SSZ-31, SSZ-42, SSZ-48, CIT-5, UTD-1 and VPI-5) are investigated with hydrocarbon adsorption using a series of adsorbates with varying molecule sizes. Valuable input from adsorption for the determination of zeolite structures is demonstrated with zeolite SSZ-42 that contains an undulating, one-dimensional 12-MR channel system. The adsorptive properties of two newer zeolites with unknown structures, SSZ-53 and SSZ-55, are discussed. The observed adsorptive characteristics provide useful information for the structure characterization of novel zeolites.
223
17-P-08- Different chemisorption methods applied to zeolite supported Pt-catalysts J.C. Groen (a), J. P6rez-Ramirez (b) and L.A.A. Peffer (a) a Applied Catalyst Characterization, b Industrial Catalysis, Delft University of Technology, j. c.groen@tnw, tudelft, nl, The Netherlands. Chemisorption measurements of hydrogen and carbon monoxide on zeolite supported Ptcatalysts have been studied by the static volumetric adsorption method and the dynamic pulse adsorption method. Zeolites with different pore size and Si/A1 ratio have been investigated and compared to traditional supports such as A1203 and SiO2. Both methods show an excellent agreement for determination of the metal dispersion for low and highly-dispersed Pt-catalysts, using CO and H2. Weak gas-metal-support interactions did not influence the results achieved. Application of the extrapolation procedure in the static volumetric adsorption method is strongly discouraged.
17-P-09 - Structure
vs.
adsorption properties of 5A zeolites
H. Paoli (a), T. Bataille (), B. Rebours ta), A. M~thivier (a) and H. Jobic (b) alnstitut Franqais du P6trole, [email protected], Rueil-Malmaison, France bInstitut de Recherches sur la Catalyse, CNRS, Villeurbanne, France To correlate the adsorption and diffusion properties to the cation distribution in the structure of CaNaA zeolites, temperature programmed desorption, anomalous X-ray powder diffraction and quasi elastic neutron scattering experiments were performed. It is shown that water adsorption and diffusion behaviour differs with the calcium content. Fourier maps obtained from anomalous diffraction experiments near the Ca K-edge allow to identify the calcium crystallographic sites unambiguously.
17-P-10- Hydrogen adsorption in lithium exchanged Na A zeolites S. Kayiran, F. Darkrim* and A. Gicquel Laboratoire d'Ing~nierie des Mat~riaux et des Hautes Pressions, LIMHP CNRS UPR n~ 99 Av. J. B. Cldment 93430 Villetaneuse, France, [email protected] 3.fi" The present work is devoted to the analysis of the influence on gas adsorption of the crystal structure modifications by ionic exchanges of the dehydrated Li A zeolite. We studied the hydrogen adsorption under pressure up to 1 MPa and at room temperature on the NaA zeolite and on its fully and partially lithium exchanged forms. The Na A zeolite is prepared by hydrothermal method, and its ionic exchange in different level by lithium is obtained by successive contacts. The structural characterisations have been evaluated by Scanning Electronic Microscopy (SEM), X Ray Diffraction (XRD), Nuclear Magnetic Resonance (NMR), Atomic Absorption and helium density measurements. We noted that there was no loss of crystallinity after ionic exchange in the zeolites. The hydrogen adsorption capacity varied with the increase of the cation exchange rates. Hydrogen adsorption is due to sterical effects and gas-solid molecular interactions which are intimately linked to the adsorbent structure modifications and the chemical nature of cations containing zeolite.
224
17-P-I 1 - M a c r o s c o p i c and microscopic investigations of the interaction of a chloroalkene on a MFI zeolite v. Frangois, S. Maure, F. Bouvier, G. Weber, O. Bertrand, J.P. Bellat and C. Paulin
Laboratoire de Recherches sur la R6activit~ des Solides, Do'on, France Guy. weber@u-bourgogne,fr Gravimetric, microcalorimetric, in-situ XRD and in-situ FTIR spectroscopic studies of the interaction of trichloroethene and tetrachloroethene on high siliceous zeolites were carried out to look further into knowledge of adsorption processes of large admolecules in the microporous network of MFI adsorbents. Trichloroethene gives classical type I isotherms whereas tetrachloroethene gives stepped isotherms at 298 K. Furthermore, structural changes of the adsorbent were observed for the adsorption of either trichloroethene or tetrachloroethene. A comparative analysis of macroscopic and microscopic data is proposed and correlations are established between thermodynamic and structural data.
17-P-12 - Sorption and pore condensation behavior of pure fluids in mesoporous M C M - 4 8 silica, M C M - 4 1 silica and controlled pore glass M. Thommes l, R. K6hn 2 and M. Fr6ba 2'3
I Quantachrome GmbH, Rudolf-Diesel-Strafle 12, 85235 Odelzhausen, Germany 2 Inst. oflnorg. Chem., University of Hamburg, Hamburg, Germany 3 Inst. oflnorg. Chem., University ofErlangen-Nuremberg, Erlangen, Germany A systematic study of the sorption and pore condensation behavior of nitrogen, argon and krypton in various silica materials (MCM-48, MCM-41 and Controlled Pore Glass (CPG)) at 87 and 77 K is presented. A detailed characterization with respect to surface area, pore volume and pore size distribution together with a comparison of sorption hysteresis in MCM48 and MCM-41 silica materials of nearly equal pore size has been performed. In addition we focus on the sorption and phase behavior of argon and krypton below the bulk triple-point temperature.
17-P-13 - Pore size analysis with H 2 0 adsorption organically modified M C M - 4 1 type materials
measurement
of
N. Igarashi (a), K. Nakai (b), K. Hashimoto (a) and T. Tatsumi (c)
aThe University of Tokyo, Tokyo, Japan; bBel Japan, Inc., Osaka, Japan Cyokohama National University, Yokohama, Japan, ttatsumi@ynu, ac.jp. Hexagonally structured mesoporous molecular sieves (MCM-41) containing organic groups have been synthesized under various conditions and were used to test the applicability of the Kelvin equation to water adsorption. It was shown that the pore size estimation, assuming the Kelvin equation corrected for the statistical film thickness of H20, is in quite good agreement with that obtained with N2 adsorption for the relatively hydrophilic samples when the appropriate value of the radius of curvature of the meniscus was used. The correction of contact angle of curvature of the meniscus was necessary for the hydrophobic materials in order to match the pore sizes estimated on the basis of H20 adsorption to those obtained by N2 adsorption.
225 1 7 - P - 1 4 - Adsorption of carbon dioxide b y X zeolites exchanged with Z n 2+
and Cu 2+" isosteric heat and adsorption isotherms A. Khelifa (a), Z. Derriche (b) and A. Bengueddach (c) a Laboratoire S.T.E.V.A., B. P. 1001, R. P., Mostaganem, Telefax." +213 45 21 10 18, Alg6rie. b Laboratoire ale physico-chimie ales mat~riaux, U. S. T. Oran, Alg6rie. c Laboratoire de chimie des mat6riaux, Universit~ d'Oran, Alg~rie. Adsorption of C02, at intervals of 30 K between 303 and 363 K, has been carried out on M2+X zeolites (Mz+=zn 2+ or Cu 2+) exchanged at different degrees. Analysis of the isosteric heat reveals a character energetically heterogeneous only for NaX and Zn(x)X exchanged at higher degree and at low coverages. Several models have been used to describe the experimental isotherms. The best fit of adsorption isotherm data is obtained with the Sips model, while the adsorbed phase would be localised on adsorptive centres and is subject to minor adsorbateadsorbate interactions. These interactions have repulsive character.
1 7 - P - 1 5 - A combination of high resolution manometry, gravimetry and microcalorimetry to study the co-adsorption of Ar/N2 mixtures on 5A and 13X zeolites S. Moret, F. Rouquerol, J. Rouquerol and P.L. Llewellyn MADIREL, CNRS/University of Provence, Marseille cedex 3, France. The adsorption of three argon/nitrogen binary mixtures at 310 K and up to 0.6 bar are presented. A continuous, quasi-equilibrium flow technique of adsorptive introduction was used to allow high-resolution isotherms to be obtained. These are compared to differential enthalpies of adsorption determined using adsorption microcalorimetry.
1 7 - P - 1 6 - Gas adsorption microcalorimetry on zeolites under supercritical
conditions up to 15 bars T. Poyet, F. Rouquerol, J. Rouquerol and P.L. Llewellyn MADIREL, CNRS/University of Provence, 26 rue du 141 ~meRIA, 13331 Marseille cedex 3, France. The adsorption of nitrogen on silicalite, DAY and NaX at 310 K was carried out up to a pressure of 15 bars. Combined manometric and microcalorimetric measurements were carried out under high-resolution conditions. The isotherms show a marked deviation from Henry's law behaviour.
226
18- Adsorption and Separation Process (Monday) 18-P-06 - Evaluation of mesoporous silicas as stationary phases for high performance liquid chromatography (HPLC) L. Sierra (a), B. Lopez (a), A. Ramirez (a) and J.-L. Guth (b)
a Departamento de Quimica, Universidad de Antioquia, Medellin, [email protected], Colombia; b Laboratoire de Matdriaux Min~raux UPRES-A 7016, Universitd de Haute Alsace, Mulhouse Cedex, France. Four mesoporous silicas, formed of isometric particles with 2.8 nm and 5.6 nm pores, were prepared by varying the synthesis conditions (silica source, surfactant, pH and temperature). A part of each sample was silylated with C8 chains. The silanol and silyl groups contents were estimated by 29Si NMR. Good separations have been obtained on mixtures of aromatic molecules by normal-phase HPLC with the four materials. In reversed-phase HPLC the results exhibit differences in function of the pore filling by the silyl groups.
18-P-07 - Adsorption of N-nitrosamines by zeolites in solutions Ying Wang, J.H. Zhu*, D. Yan, W.Y. Huang and L.L. Ma
Department of Chemistry, Nanjing University, Nanjing 210093, China Zeolite could selectively adsorb N-nitrosamines in the solution of methylene chloride or water, and the equilibrium data were fitted to Freundlich-type isotherms. Textural and acidbasic properties of zeolite determined their adsorption capacity. The extraordinary adsorption properties of NaA zeolite for N-nitrosamines is inferred that the adsorbates inert the channel with the group-N=N-O. Larger amount of N-nitrosamines was adsorbed on ZSM-5 zeolite in water instead in methylene chloride, due to the hydrophobicity of the zeolite. Application of zeolite to remove N-nitrosamines from beer seems successful. Up to 100% of the worst carcinogenic compounds could thus be removed with 1.4 g/L of zeolite which was proven to be better adsorbent than silica or alumina. On Na[3 zeolite and MCM-41 mesoporous material N-nitrosodimethylamine decomposed above 573 K and the liberated NOx could be detected even at 773 K during the TPSR process, indicating the strong adsorption of N-nitrosamines on molecular sieves that makes zeolite become the functional materials for environmental protection.
18-P-08 -An adsorption-desorption process for separation of C8 aromatics G.-Q. Guo (a, b) and Y.-C. Long (b*)
a Research Institute ofBeijing Yanshan Petrochemical Corporation, SINOPEC, Beijing 102500, P.R. China, [email protected] b Department of Chemistry, Fudan University, Shanghai 200433, P.R. China An adsorption-desorption process has been developed through the study of static equilibria of C8 aromatics in liquid phase. The binder-free adsorbent used is high silica MFI type zeolite, which possesses high hydrophobicity. Six organic compounds as desorbents matched with the adsorbent were screened. The competitive adsorption curves of multi-component feed were also investigated.
227
18-P-09 - Preparation of Na-A zeolite capillary columns by in-situ synthesis D. Kou, Z. Li, J. Wu, Ming Liu and S. Xiang*
Department of chemistry, Nan Kai University, Tianjin, P.R. China- [email protected] The traditional zeolite PLOT column has lots of shortcomings, which considerably restrict the further development of zeolite in practical utilization. In this paper, a new kind of NaA zeolite GC column has been prepared and characterized by in-situ synthesis technique. The form process and mechanism in capillary column have also been discussed. On the basis, gas-solid and gas-liquid capillary columns have been prepared, which both show good separation of various organic compounds and extensively broaden the range of the utilization of zeolite in GC. Furthermore, the zeolite large bore column has also been prepared and the test result is very good. Consequently, the possibility to replace packed column in a great deal of regular analysis has been pursued.
18-P-10 - Adsorption of CO2, SO2 and NH3 on zeolitic materials synthesized from fly ash S. Hernfindez (a), R.Juan (a), X. Querol (b), N. Moreno (b), P. Ferrer (a) and J.M. Andr6s (a). a Instituto de Carboquimica (CSIC), [email protected], Spain. b Instituto de Ciencias de la Tierra ((Jaume Almera))(CSIC), [email protected]'a.csic.es, Spain Zeolites synthesized from fly ash were selected for determining the adsorption capacity of CO2, SO2 and NH3 and the surface area. The results showed a low retention capacities for Sodalite, Analcime, NAP1, F Linde and KM (3.2-9.3 mg CO2/g, 1.1-3.9 mg SO2/g and 0.5-4.8 mg NH3/g) that could be explained for the low Sco2 measured in the working conditions (2347 m2/g). High retention capacities were found for Herschelite and Zeolite A by the same technique (30.3-73.5 mg CO2/g, 9.3-21.7 mg SO2/g and 8:1-110.7 mg NH3/g). The results suggest a certain relationship between surface area and adsorption capacities.
18-P-II structure
Dibenzothiophene
adsorption
over
zeolites
with
faujasite
J.L. Sotelo, M.A. Uguina, M.D. Romero, J.M. G6mez, V.I. Agueda and M.A. Ortiz.
Chemical Engineering Department. Faculty of Chemistry. Complutense University of Madrid, Madrid, Spain. [email protected], ucm. es Adsorption of dibenzothiophene (DBT) over FAU zeolites exchanged with alkali cations has been studied. Cristallinity (by XRD and IR), exchange level (XRF) and basic properties (CO2 TPD) of different adsorbents used have been determined. The influence of Si/A1 molar ratio and type of cation exchanged in the zeolite as well as the presence of toluene in feedstock mixture on DBT adsorption capacity and selectivity of adsorbent has been also determined. Thermogravimetric analysis showed a stronger DBT adsorption over X zeolites.
228
18-P-12 - Pressure swing adsorption of ethyl acetate on silica MCM-41 S. Namba (a), D. Yomoda (a), J. Aoyagi (a), K. Minagawa (a), T. Kugita (a) and J. Izumi (b) a Teikyo University of Science & Technology, Yamanashi, [email protected], Japan. b Nagasaki R & D Center, Mitsubishi Heavy Industries, Ltd., Nagasaki, Japan. Fundamental studies on removal/recovery of ethyl acetate vapor from industrial waste effluent gas by pressure swing adsorption (PSA) on silica MCM-41 were made. From effects of pretreatment temperatures (673-1073 K) and trimethylsilylation it is found that ethyl acetate molecules are irreversibly adsorbed on surface -OH groups on silica MCM-41 through hydrogen bonding at a low adsorption/desorption temperature of 303 K. With increasing adsorption temperature from 303 to 373 K the amount of irreversible adsorption decreased to almost nil. Therefore a combination of PSA and temperature swing adsorption operation is desirable for remove/recovery of ethyl acetate vapor. The reversible adsorption capacity becomes 250 mg g~ by the combination.
18-P-13 - P occlusion in LTA: an approach for enhancing N2 adsorption properties L. Johnson and M. Miller Air Products & Chemicals, Inc., Allentown, PA, USA, [email protected] Ca ion exchange treatments and thermal activation of ZK-21 with different P and A1 contents prepared the materials for adsorption studies. The activated CaZK-21 materials contain both occluded P and framework substituted P. The relative amounts of occluded P and framework P change with the starting composition of the ZK-21 and the post synthetic treatment. The N2 Henry's Law constant (KH N2) at 23 ~ and the Henry's law N2 selectivity (KHN2/KHO2) at 23 ~ increase with increasing amounts of occluded P in the CaZK-21 materials and are independent of Ca content, indicating the occluded P is enhancing the effectiveness of the available Ca for N2 adsorption. CaZK-21 with 5.1 occluded P/unit cell achieves the same KH N2 at 23 ~ as CaLTA, even though the CaLTA contains 50% more Ca cations.
18-P-14 - Sulfur guard bed material from local bentonite deposits S. Mikhail and T. Zaki Egyptian Petroleum Research Institute - Nasr City- Cairo - Fax No." O0 202 2747433-Egypt. The new preceding step in the catalytic hydrotreating process is the application of a guard bed adsorbent in the refinery, to get a product containing least amount of sulfur, which is necessary for making an acceptable feed for steam refining process. This work deals with the study of the preparation of sulfur guard bed from locally cheapest material. Guard bed is prepared by loading the more efficient adsorbent bentonite clay with high capacity nickel for the removing of trace sulfur. The nickel was anchored in the silicate layered clay structure via new technique "electroless technique" to assure the realization of a fine dispersion and a maximum homogeneous distribution of the active nickel metal on the clay surface area. The structure of the original clay and the prepared guard bed has been studied physically and chemically by applying different techniques: x-ray analyses, thermal analyses, acidity and pore size distribution.
229
18-P-15- Simulation for removal of binary solvent vapor by adsorption onto high silica zeolite K. Chihara, T. Saito, H. Suzuki, H. Yamaguchi and Y. Takeuchi
Dept. of Ind. Chem, Meij'i University, 1-1-1 Higasi-Mita, Tama-ku, Kawasaki, Japan Adsorption of some organic solvent vapours onto HSZ were studied. Binary adsorption equilibriums except azeotropic mixture-HSZ systems could be correlated by MarkhamBenton equation for the whole concentration range, and the break times could be estimated well by using the Extended-MTZ-Method. For azeotropic mixture-HSZ systems, the equilibriums and the break times could be correlated and estimated only for a part of the all concentration range. Then, two azeotropic points appeared in the adsorption equilibriums for IPA-TCE -Y-type system. For this binary systems adsorption equilibrium data could be expressed by proposed equation, similar to liquid-vapour azeotropic equilibrium equation. Breakthrough curve could be simulated using the Stop&Go method in the whole range for azeotropic mixture systems as well as for zeotropic systems.
230 23 - Micro- and Mesoporous Materials in Fine Chemistry (Monday)
Selective hydroxyethylation of furfuryl alcohol with aqueous acetaldehyde in the presence of H-form zeolites
23-P-06-
A. Finiels, W. Balmer and C. Moreau
UMR 5618 ENSCM-CNRS, E. N. S. C. Montpellier, France- [email protected] Hydroxyethylation of furfuryl alcohol with aqueous acetaldehyde was performed at 318 K in the presence of FAU, MOR and MFI zeolites in their protonic form. Besides the hydroxyethylation reaction, two other parallel reactions may compete, i.e. oligomerisation of acetaldehyde and resinification of furfuryl alcohol. The former reaction is easily controlled over a MFI catalyst with a Si/A1 ratio of 25 but the latter is not, and linear furanic polymers, capable of deactivating the catalyst, were often formed. A selectivity of about 55 % in the carbinol intermediate was initially achieved in the presence of the MFI (25) catalyst for a furfuryl alcohol conversion up to 65 %. However, after optimization of the kinetic parameters, the selectivity is increased to 95 %, but to the detriment of furfuryl alcohol conversion. 2 3 - P - 0 7 - Selective synthesis of monooctylamines by ammonia alkylation with octanol using NaY, ZSM-5, SAPO-5, SAPO-II, SAPO-31, SAPO-34 S. Amokrane (a), R. Rebai (a), S. Lebaili (b), D. Nibou (b) and G. Marcon (c) a Institut de Chimie Industrielle, fax ." 022132247182, Alger, Algerie b Institut de Gdnie Mdcanique, fax ." 022132247182, Alger, Algerie. c L TPCM/INPG/CNRS, gmarcon@ltpcm, inpg.fr, St. Martin d'HOres, France. This work deals with the synthesis of monooctylamines by ammonia alkylation with octanol-I in gaseous phase using various catalysts. These microporous materials were prepared by the hydrothermal method. Y-faujasite and ZSM-5 supports were exchanged by lead and uranyl ions at different concentrations in order to increase their surface acidity necessary for reaction mechanism. The obtained results show that the use of these catalysts results in the formation of primary amines. Monooctylamines selectivities of 90 % were obtained in the present work. It was observed that when SAPO-34 is used, the trioctylamine isomer could be formed in the external surface of the catalyst.
Conversion of monoethanolamine in other organic nitrogen compounds on H-mordenite and H-clinoptilolite 23-P-08-
G. Torosyan, S. Sargsyan and A.Grigoryan State Engineering University of Armenia, Yerevan, Armenia, [email protected]. The synthesis of ethyleneimine from monoethanolamine over H-mordenite and H-clinoptilolite has been studied. The natural zeolites of Armenia were used as support. The proposal method synthesis has advantages over the Wenkler ethyleneimine synthesis: no using of acidic corrosion equipment and disposal of waste water containing sulfuric acid. It has been formed piperazine and its derivatives as by-products. The last nitrogen compounds are formed generally with monoethanolamine excess in reaction conditions. In this case, for these compounds formation has been proposed three pathways. It was investigated the adsorption of amine substrate when using zeolites too.
231
23-P-09 - The influence of ammonia adsorption on Y Zeolite and natural clinoptilolite activity in ethanol transformation L. Akhalbedashvili (a), A. Mskhiladze (b) and S. Sidamonidze (a)
a Tbilisi State University, 380028, 3 Ave. Chavchavadze, e-mail." [email protected]., Tbilisi, Georgia," b Sukhumi State University, Jikia, 12, Tbilisi, Georgia The effect of NH3 adsorption on catalytic activity and selectivity of cation-exchanged Y zeolite and natural clinoptilolite (deposit of Georgia) in ethanol transformation was investigated. The ODH of alcohol is accompanied by dehydration to ethylene and diethylether and deep oxidation to CO2. NH3 blocks the acidic active centers of dehydration of Y zeolites and promotes the oxidative activity of samples with transition metal cations. The influence of the ion nature for the catalytic transformation of ethanol was shown by a considerable increase of carbon dioxide formation after NH3 adsorption. The cation associated has been destroyed under NH3 influence, and NH3 formed with cations coordinated-unsaturated complexes.
2 3 - P - 1 0 - Enantioselective synthesis and separation of terminal epoxides and diols using a catalytic membrane system containing chiral Co(III) salen S.-D. Choi and G.-J. Kim
College of Engineering, Inha University, Inchon, Korea, kimg/@inha.ac.kr The importance to use optically pure isomers as pharmaceuticals, food additives, agrochemicals, (etc) is becoming more and more evident. The classical resolution still accounts for a large part of chiral production, however the asymmetric synthesis and the use of chiral separation system one becoming increasingly popular. The enantioseletive hydrolytic resolution of racemic epoxides was performed in the ZSM-5/MCM-41 membrane system containing chiral salen complexes. The chiral salen complexes immobilized on the membrane showed a very high enantioselectivity in the hydrolysis of epichlorohydrine, epoxybutane, styrene oxide and 1,2-epoxyhexane.
23-P-11 - Asymmetric trimethylsilylcyanation of benzaldehyde catalyzed by chiral Ti(IV) salen complexes immobilized on MCM-41 J.-H. Kim and G.-J. Kim
Department of Chemical Engineering, College of Engineering, Inha University, Inchon 402-751, KOREA, kimg]@inha.ac.kr The efficiency of new unsymmetrical chiral salen ligands was examined in the asymmetric trimethylsilylcyanation of benzaldehyde. A very high level of enantioselectivity was attainable over chiral Ti(IV) salen complexes prepared from salicylaldehyde and 3,5-Di-tertbutylsalicylaldehyde derivative as compared to the conventional salen catalyst. Enantiomeric excess of the corresponding reaction product was generally more than 70% over unsymmetric chiral salen catalysts. The chiral Titanium(IV) salen complexes immobilized on a mesoporous MCM-41 by multi grafting method showed a relatively high enantioselectivity for the addition of trimethylsilyl cyanide to the benzaldehyde.
232
23-P-12 - Mechanistic study of aniline methylation over acidic and basic zeolites Y I.I. Ivanova (a), E.B. Pomakhina (a), A.I. Rebrov (b), Y.G. Kolyagin (a), M. Hunger (c) and J. Weitkamp (c) a Moscow State University, Moscow 119899, e-mail. [email protected] b Institute of Petrochemical Synthesis, RAS, Leninsky pr. 29, 117012 Moscow, Russia c Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany 13C MAS NMR has been performed in-situ under batch conditions to investigate the mechanism of aniline alkylation with methanol on acidic H-Y and basic CsNa-Y impregnated with cesium hydroxide. On acidic zeolite H-Y, methanol reacts with zeolitic hydroxyl groups to give surface methoxy groups which, in turn, play a role as alkylating species in aniline methylation. On the basic zeolite Y, methanol is converted into formaldehyde, which is responsible for the Nalkylation. Both on acidic and basic zeolites, N-methylaniline is the primary alkylation product. Toluidines and N-methyltoluidines are formed only on the acidic zeolite at elevated temperatures after complete conversion of methanol into N-methylaniline.
23-P-13 - Heterogeneous base catalysis: characterization of zeolites and mixed oxides using nitromethane as a N M R probe molecule and activity in the Michai~i condensation of nitromethane and cyclohex-2-en-l-one E. Lima, L.-C. de Mtnorval, M. Lasptras, J.-F. Eckhard, D. Tichit, P. Graffin and F. Fajula Ecole Nationale Sup6rieure de Chimie de Montpellier, [email protected] The use of nitromethane as a probe of basicity of zeolites (NaX, CsX, CsX 9Cs) and mixed oxides, Mg(AI)O, is discussed. Various species (physisorbed nitromethane, aci-anion nitromethane, and methazonate salt analogue) formed upon nitromethane adsorption were characterized by 13C MAS NMR spectroscopy. Heterogeneous base catalysis of the Michael addition of nitromethane on cyclohex-2-en-l-one was also studied. Low rates were obtained for catalysts showing only nitromethane physisorption. Formation of aci-anion nitromethane was observed for solids of medium efficiency; correlation of the chemical shift with the initial rate was established. Finally, the decrease of Lewis acidity and concomitant increase of basicity led to methazonate formation and to the more efficient catalysts.
23-P-14 - Synthesis molecular sieves
of ot-pinene
derivatives
using
redox-mesoporous
Y.-W. Suh (a), T.-M. Son (a), N.-K. Kim (b), W.-S. Ahn (b) and H.-K. Rhee* (a) a School of Chemical Engineering and Institute of Chemical Processes, Seoul National University, Kwanak-ku, Seoul 151-742, [email protected], Kore a b School of Chemical Science and Engineering, Inha University, Inchon 402-751, Korea Ti-HMS catalyst was successfully used as a bifunctional catalyst for the one-step conversion of a-pinene to campholenic aldehyde.
233
23-P-15 - Ring opening reactions of methyloxirane over D Z S M - 5 D A I M C M - 4 1 molecular sieves - A mechanistic study
and
A. Ffisi (a), I. Pfilink6 (b), A. G6m6ry (a) and I. Kiricsi (c)
a Chemical Research Center of the HAS, P.O. Box 17, Budapest, H-1525 Hungary b Department of Organic Chemistry, c Department of Applied and Environmental Chemistry, University of Szeged, D6m t6r 8, Szeged, H-6720 Hungary, [email protected] The ring opening reactions of methyloxirane (single C-O scission and dimerization were the main transformation channels) on DZSM-5 and DA1MCM-41 aluminosilicates were studied in a pulse microreactor at 363 K. Deuterium distribution in the products was monitored. For deuterium exchange to occur during ring opening at least one Bronsted site is necessary. For the formation of deuterium-exchanged dioxolane derivatives two neighbouring BronstedLewis site pairs, while for the formation of deuterium-exchanged dioxane derivatives the interplay of a Bronsted-Lewis acid pair and a Lewis-Lewis acid pair seem to be the most advantageous.
2 3 - P - 1 6 - Hydrodechiorination of 1,2,4-trichlorobenzene on Ni/AI-MCM-41 catalysts Y. Cesteros (a), P. Salagre (a), F. Medina (b), J.E. Sueiras (b) and G.L. Hailer (c)
a Facultat de Quimica. Universitat Rovira i Virgili, Tarragona, [email protected], Spain. b Escola d'Enginyeria Quimica. Universitat Rovira i Virgili, Tarragona, Spain.. c Department of Chemical Engineering. Yale University, USA. Several Ni/A1-MCM-41 catalysts were prepared by the incipient wetness method followed by calcination and reduction. These catalysts are highly active (100%) and selective (100%) towards benzene in the hydrodechlorination of 1,2,4-trichlorobenzene in the gas phase at mild conditions of work: 1 atm pressure and reaction temperatures between 473-523K. This catalytic behaviour has been correlated with the structural characteristics of the catalysts.
23-P-17 - Adsorption of cytochrome c onto ordered m e s o p o r o u s silicates J. Deere, E. Magner, J.G. Wall and B.K. Hodnett.
Department of Chemical and Environmental Sciences, Materials and Surface Science Institute, University of Limerick, Limerick, [email protected], Ireland. Adsorption and desorption characteristics of the protein cytochrome c onto ordered mesoporous silicates are detailed. The amount of adsorption is related to the characteristics of the mesopore diameter with most adsorption associated with materials having pore diameters in excess of the size of cytochrome c. Adsorbed protein did not desorb with repeated washing in buffer but polyethylene glycol and/or ammonium sulphate in buffer caused considerable desorption.
234
23-P-18 - Vapor phase Beckmann rearrangement of cyclohexanone oxime over tantalum pillared magadiite S.J. Kim (a), M.H. Kim (a), Y. Ko (a), G. Seo (b) and Y.S. Uh (a) a KIST, P.O. Box 131, Cheongryang, Seoul 130-650, uhvoun~kistmail.kist.re.kr, Korea b Chonnam National University, Kwang/u 500-757, Korea Vapor phase Beckmann rearrangement of cyclohexanone oxime to e-caprolactam has been carried out using tantalum-pillared magadiites (Ta-magadiites) with different surface areas as catalysts. The Ta-magadiite catalysts of relatively large surface areas showed high catalytic activities, due to a large number of active sites. For the Ta-magadiite catalyst of the largest surface area, the oxime conversion reached 99.1% with 97.5 % of lactam selectivity. FT-IR and NH3-TPD results demonstrated that the new hydroxyl groups and a large amount of acidic sites generated by Ta pillaring into the magadiite interlayer were responsible for the high catalytic performance of Ta-magadiite catalyst.
23-P-19 - Hydration of cz-pinene over heteropolyacids encaged in USY zeolites J. Vital a*, A.M. Ramos a, I.F. Silva a, J.E. Castanheiro a, M.N. Blanco b, C. Caceres b, P. Vasquez b, L. Pizzio b and H. Thomas b CQFB, Faculdade de Ci~ncias e Tecnologia, Universidade Nova de Lisboa, 2825-114 CAPARICA, Portugal. E-mail."[email protected], unl.pt b Conicet, UNLP, Cindeca 47, n ~257, 1900 La Plata, Argentina The catalytic performance of dodecamolibdophosphoric acid (PMol2) encaged in the supercages of zeolite USY or silica supported, was compared concerning the hydration of otpinene in aqueous acetone at 50 ~ C. A selectivity value of 75%, towards cz-terpineol, was achieved with the encaged PMol2, at total conversion. Selectivity values obtained with the encaged catalyst are similar to those obtained with the free PMol2, but higher than those obtained with the silica supported HPA.
23-P-20 - Selective adsorption of t r a n s unsaturated fatty acid compounds in MFI type zeolites S. Paulussen, M. Goddeeris and P.A. Jacobs Katholieke Universiteit Leuven, Centrum voor Oppervlaktechemie en Katalyse, Kasteelpark Arenberg 23, B-3001 Heverlee, Belgium ([email protected]) A zeolite structure that selectively adsorbs trans unsaturated fatty acid compounds in the presence of their cis unsaturated counterparts is selected among several topologies using a liquid phase chromatographic study of the adsorption of oleic and elaidic acid methylester. The functioning of the present adsorbent is based on the restricted adsorption of the curved cis unsaturated compounds in the pores of highly siliceous MFI type zeolites while the straight trans isomers experience significantly less limitations. The present selectivity is retained when the complexity of the substrate molecules is gradually increased from methylesters to triacylglycerols.
235
23-P-21 - Novel delaminated zeolites are more active acid catalysts than conventional zeolites and mesoporous AI/MCM-41 for the synthesis of fine chemicals M.J. Climent, A. Corma,* V. Forn6s, H. Garcia, S. Iborra, J. Miralles and I. Rodriguez
ITQ-CSIC-UPC, Universidad Polit6cnica de Valencia, Valencia, Spain. Fax 34 96 3877807. ITQ-2 zeolite prepared by delamination of MCM-22 precursor, is formed by disordered individual sheets of crystalline zeolitic layers in where the Bronsted acid sites are of zeolitic nature and the vast majority of them accessible to large molecules. The delaminated zeolite combines the acid characteristic of microporous zeolites with accessibility of the sites of mesoporous A1/MCM-41 and amorphous silica-alumina. The superior catalytic performance of delaminated zeolites compared to conventional zeolites and A1/MCM-41 is examplified for reactions involving large reactant molecules, namely: the preparation of dimethyl acetals, the Beckmann rearrangement of bulky cycloalkanone oximes and hydroxylation of aromatics.
23-P-22 - The design of zeolites catalysts for the synthesis of orange blossom and apple fragrances M.J. Climent, A. Corma and A. Velty
Instituto de Tecnologia Quimica (UP v-csIc). Universidad Polit6cnica de Valencia. Avenida de los Naranjos s/n, 46022, Valencia, Spain. The synthesis of propylene glycol acetal of methylnaphthyl ketone and ethylene glycol acetal of ethyl acetoacetate, which are flavouring materials with orange blossom and apple scent respectively, have been obtained successfully in presence of different zeolites. It has been found that a higher concentration of acid sites in the catalyst does not guarantee a better catalytic performance and for acetalization reaction the hydrophobic properties of catalyst are as important as the concentration of active sites. This work presents the crucial role that the control of the textural and adsorption properties play in optimizing a zeolite catalyst for the production of these two fragrances.
23-P-23 - Catalytic in-situ infrared spectroscopic study of n-butyraldehyde aldol condensation U. Rymsa, M. Hunger and J. Weitkamp
Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany Aldol condensation of n-butyraldehyde on cesium-exchanged zeolites X and Y, mesoporous MCM-41 and silica gel impregnated with cesium salt yield initially 2-ethylhexenal with 100 % selectivity at a high conversion. The active catalysts suffer from fast deactivation, which is probably caused by a Tishchenko side reaction leading to the formation of butyric acid. A carboxylate ion strongly adsorbed on the catalyst surface is detected by in-situ infrared spectroscopy. It probably poisons the active sites and furthermore blocks the pores of microand mesoporous catalysts. Carboxylate formation cannot be suppressed by carrying out the reaction in hydrogen or by adding water to the feed. However, complete catalyst regeneration can be achieved by heating in nitrogen at around 350 to 400 ~
236
2 3 - P - 2 4 - Oxyhalogenation of aromatic compounds in presence of KCI or KBr and H202 over zeolites N. Narender, P. Srinivasu, S.J. Kulkarni and K.V. Raghavan
Catalysis Group, Indian Institute of Chemical Technology, Hyderabad, India The oxychlorination and oxybromination reactions of aromatic compounds were carried out over modified Y and ZSM-5 zeolites in presence of KC1 or KBr and H202. The process is facile and ecofriendly and the catalyst can be reused. In the oxychlorination of phenol, the yields of para chloro- and ortho chloro phenol were 63.0% and 22.0% at 85% conversion, over CeZSM-5(30) catalyst. CeZSM-5 is a better catalyst for oxychlorination compare to HZSM-5 and modified Y zeolites. In the oxybromination of aniline the yields of para bromoand ortho bromo aniline were 76.0% and 15.0% respectively at 91.0% conversion over HZSM-5 catalyst in presence of KBr and H202. The performance of HZSM-5 was better than HY and SIO2/A1203 and in absence of H202 or catalyst the conversion was less. The work using titanium zeolite or other redox system and oxidant is in progress
2 3 - P - 2 5 - Synthesis and characterization of mesoporous Pt-MCM-41 and its application in enantioselective hydrogenation of l-phenyl-l,2-propanedione E. Toukoniitty a, B. Sevcikovfi a, N. Kumar a, P. M~iki-Arvelaa, T. Salmi a, J. V~,yrynenb, T. Ollonqvist b, E. Laine c, P.J. Kooyman ~ and D.Y. Murzin a
~ of Industrial Chemistry,/[bo Akademi, Turku, Finland," bDe])artment of Applied Physics; CDepartment of Physics, University of Turku, Turku, Finland, "National Centre for HREM, Delft University of Technology, Delft, The Netherlands Pt-MCM-41 with three different Pt contents was synthesized, characterized and tested in enantioselective hydrogenation of 1-phenyl-l,2-propanedione. The maximum enantiomeric excess (ee) of (R)-l-hydroxy-l-phenylpropanone was 44% with the 15 wt.% Pt-MCM-41 modified with (-)-cinchonidine (compared to 54% obtained with 5 wt.% Pt/A1203). The highest ee obtained with 15 wt.% Pt-MCM-41 was due to the slightly larger Pt particles. Further optimization of the reaction conditions is a very important task in order to utilize mesoporous materials in enantioselective hydrogenation.
23-P-26- Isomerization of p-eugenol on palladium-containing zeolites Ts.M. Ramishvili, M.K. Charkviani and L.D. Kashia
P.G. Melikishvili Institute of Physical and Organic Chemistry, Georgian Academy of Sciences, Tbilisi, Georgia - dmk [email protected] The Y, 13 and M zeolites with SIO2/A1203 ratios of 3.9, 24 and 32, respectively, produced via recrystallization from the natural clinoptiolite in palladium form ( 0 . 6 2 - 6.16% Pd) at 413458K in He, H2 and air atmosphere isomerize p-eugenol basically into trans-isoeugenol with 70-93% selectivity; dihydroeugenol is also produced in the H2 atmosphere. The Pd-forms M and 13 are most active in the He atmosphere. Induction period at the beginning of the reaction observed in the helium atmosphere at temperature over 425 K is reduced in the air atmosphere and with 2-6% Pd content in the catalyst the condensation and oxidation reactions are rather intensive.
237
23-P-27 - T h e use of M C M - 2 2 as catalyst for the B e c k m a n n - r e a r r a n g e m e n t of c y c l o h e x a n o n e oxime to s-caprolactam G. Dahlhoff, U. Barsnick, W. Eickelberg and W.F. H61derich Heterogeneous Catalysis, RWTH, Aachen, [email protected], Germany A variety of catalysts have been applied to the Beckmann-rearrangement of cyclohexanone oxime to s-caprolactam. Experiments with MFI structures yielded good results showing the importance of weak acidic sites, a large outer surface and pore structure accessible only through 10MR channels. Recent reports recommended the MCM-22 catalyst with its large outer surface and special structure for the use in the Beckmann-rearrangement. In the present study the synthesis and brief characterisation of MCM-22 was carried out followed by the first in depth analysis of its applicability for the Beckmann rearrangement of cyclohexanone oxime to s-caprolactam. The performance of the material was compared to one of the established catalysts - the [B]-MFI - showing several drawbacks like lower yields.
23-P-28 - Nickel supported on zirconium doped m e s o p o r o u s silica as catalysts for the gas phase hydrogenation of acetonitrile P. Braos-Garcia, L. Diaz, P. Maireles-Torres, E. Rodriguez-Castelldn and A. Jim~nez-L6pez Departamento de Quimica Inorgdnica, Cristalografia y Mineralogia, Facultad de Ciencias, Universidad de Mdlaga, Campus de Teatinos, 29071 M~ilaga (Spain) Gas-phase hydrogenation of acetonitrile has been studied by using catalysts based on nickel supported on zirconium doped mesoporous silica. All catalysts are active in this catalytic reaction, but the activity decreases with the time, being more stable when increasing the nickel loading. After catalytic reaction, all catalysts contain nitrogen and carbon, being their percentages higher for shorter times of deactivation. Nevertheless, the activity and selectivity patterns are totally recovered after treatment with H2 at high temperature, which indicates that these nitrogen and carbon species can be totally removed from the surface of catalysts by hydrogenation.
23-P-29 - Synthesis of fine chemicals intermediates over basic zeolites C.O. Veloso a, A.C. Pinto b, E.N. Santos c and J.L.F. Monteiro a ~NUCAT/COPPE, Universiclade Federal do Rio de Janeiro, [email protected] 6IQ, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil ClCEx, Universidade Federal de Minas Gerais, Minas Gerais, Brazil X zeolites exchanged with cesium and impregnated with cesium species were active as catalysts for the Knoevenagel reaction between the aldehyde obtained by the hydroformylation of limonene and ethyl acetoacetate. The product distribution observed has shown that other reactions were occurring, such as decarboxilation and aldol condensation reactions that also led to products of potential commercial interest. The best results were obtained for the sample with 14 cesium atoms impregnated per unit cell, at 403 K and ethyl acetoacetate / menthene molar ratio of 5. In such a condition, yields of products of interest as intermediates for fine chemicals production were as high as 90% after 4 h of reaction.
238
23-P-30 - Selective chlorination of diphenylmethane over zeolite K-L A.P. Singh* and S.M. Kale
Catalysis Division, National Chemical Laboratory, Pune-411 008, India, Fax No. +91-205893761, Email." [email protected] The liquid phase chlorination of diphenylmethane (DPM) to 4,4'-dichlorodiphenyl-methane (4,4'-DCDPM) is investigated over a number of zeolite catalysts using sulfuryl chloride as the chlorinating agent under mild reaction conditions. Zeolite K-L is found to be highly active and selective in the formation of 4,4'-DCDPM. The conventional Lewis acid catalyst AIC13 is not at all selective in this reaction. The conversion of DPM increases with time over all the catalysts. The reaction is very fast with zeolite K-L and gives almost 68 wt.% conversion after 5 min of reaction time. Also the yields of DCDPM increase with reaction time with an obvious decrease in the yields of monochlorodiphenylmethanes (MCDPM).
23-P-31 - Butylation of phenol on medium pore A I P O 4 - 1 1 , - 3 1 structures" effect of silicon incorporation
and-41
C.V. Satyanarayana, U. Sridevi and B.S. Rao
Catalysis Division, National Chemical Laboratory, Pune, [email protected], India. Butylation of phenol with tert-butylalcohol (TBA) is reported on medium pore aluminophosphates AIPO4-11, -31 and -41. Their activity is compared with their silicon substituted versions SAPO-11, -31 and -41. AIPO4 frameworks without silicon substitution were found to be active. Terminal hydroxyls in A1PO4's are active for butylation of phenol. It was found that a temperature as moderate as 140~ is sufficient for considerable butylation of phenol. However, selectivities of the industrially important 4-TBP and 2,4-DTBP are enhanced at higher temperatures. An equimolar feed concentration of phenol and TBA is optimum to yield 4-TBP and 2,4-DTBP selectively and also a lower space velocity of about lhr ~ favours this reaction.
23-P-32 - The catalytic synthesis of the glycidol from the glycerol carbonate in presence of zeolite A J.W. Yoo and Z. Mouloungui*
Ecole Nationale Sup~rieure des Ing~nieurs en Arts Chimiques Et Technologiques-Laboratoire de Chimie Agroindustrielle- UMR 1010-INRA-INPT/ENSIACET zmouloungui@ensct_fr A study on the direct synthesis of the glycidol from the glycerol carbonate was carried out in presence of the zeolite A as a catalyst and the glycerol as an initiator. The cationic/anionic ring opening-dimerization of glycerol carbonate and cyclization of the dimer to the glycidol and the carbon dioxide as gas form is proposed in the multi-phase reaction system (liquid/solid/gas). This system overcomes the difficulty of mass transfer in the meso-porous zeolite A. The yield for glycidol reached 86 % with the zeolite A and the glycerol.
239
23-P-33 - Transfer hydrogenation of unsaturated ketones catalyzed by AIisopropoxide dispersed on MCM-41 J. Wahlen, D.E. De Vos*, M. De Bruyn, P.J. Grobet and P.A. Jacobs Centre for Surface Chemistry and Catalysis, K. U. Leuven, Belgium. dirk. devos@agr, kuleuven, ac. be Aluminium alkoxides were anchored in the pores of siliceous MCM-41 type materials. The resulting catalysts were used in the hydrogen transfer reduction of c~,13-unsaturated ketones to the corresponding allylic alcohols. The most active material is obtained by exposure of MCM41 to a toluene solution of AI(OPr~)3. With benzalacetone as a model substrate, optimum reaction conditions are cyclopentanol (hydride donor), toluene (solvent), and addition of 5A molecular sieve (water trapping).
240
01 - Mineralogy of Natural Zeolite (Tuesday) 0 1 - P - 0 6 - Zeolites in impact craters M.V. Naumov
Karpinsky All-Russia Geological Research Institute (VSEGEI), mvn@mail, wplus.net Zeolites are common post-impact minerals in three giant impact craters: Popigai (mordenite, stilbite, chabazite, and heulandite), Kara (analcime with minor chabazite, laumontite, stilbite, and mordenite), and Puchezh-Katunki (heulandite, chabazite, analcime, stilbite, laumontite, with minor erionite, philippsite, and clinoptilolite). Zeolites occur mainly as fissure-filling and vugs. In the central uplift area, zeolites exhibit a vertical zonation due to the thermal gradients existing during impact-induced hydrothermal circulation whereas in the annular depression the differentiation of zeolites is caused by inhomogeneity of substrate. Zeolite formation by itself and specific features (e.g., enrichment in silica) of zeolites in impact craters are provided by the occurrence of large amounts of shock-disordered silicate matter there.
0 1 - P - 0 7 - A! ordering in a dachiardite framework M. Kato(a) and K. Itabashi(b)
(a) Research Centerfor Chemometrics, Toyohashi University of Technology, Toyohashi 4418580, Japan (b) Nanyo Research Laboratory, Tosoh Corporation, Shinnanyo 746-8501, Japan AI ordering in a dachiardite framework was examined based on the structural data and 29Si MAS NMR spectra. Obtained ordered distribution model of dachiardite contains four AI atoms per unit cell, and its space group was P2/m instead of the conventional C2/m. A1 atoms are located on T3 and T4 sites which construct 4 rings. Because AI content in a mined sample is larger than four, small amount of Si atoms should be substituted by AI atoms and some extent of AI atoms move to another site in order to satisfy the Loewenstein's rule. Simulated NMR spectrum based on this substitution was in excellent agreement with the observed ones.
OI-P-08 - Chemical composition and ion-exchange properties of a natrolite from Zahedan region, Iran A.R. Sardashti a, H. Kazemian b and M. Akramzadeh Ardakani a
~Dep. of chem. fac. of sci. Sistan & Baloochestan university, Zahedan, Iran bjaber Ibn Hayan Research Labs., AEOI, North Amir Abad Ave. Tehran 14374, Iran, e-mail" hkazemian@w~176 This paper reports on the ion-exchange behavior of a natural zeolite from Zahedan region of Iran towards various heavy metal cations. The distribution coefficients (Kd ,ml/g), equilibrium constant (Ka) and Gibbs free energy AG~ ~) were calculated from the isotherms data at at 298K and 323K as the thermodynamic parameters. The pre-purified material was natrolite rich-ore with some calcite as impurity. The ion-exchange experiments of the zeolite were performed in order to investigate its ability for removing the considered cations from industrial wastewater streams. The natrolite mineral exhibited the selectivity sequence: Ag+>>pb+2> Cd+2>Cu +2 > Zn +2 but was not promising from a pratical point of view.
241
0 1 - P - 0 9 - Physical, chemical and structural characterization of the volcanic tuff from the Maramures area, Romania R. Pode (a), G. Burtica (a), S. Herman (a), A. Iovi (a) and I. Calb (b)
a University "Politehnica" of Timisoara, Romania, Email: [email protected] b Cemacom SA, 4700 Zalau, Romania, Fax ." +40 60 661003 The present work pursued the physical, chemical and structural characterisation of the volcanic tuff that comes from the northern part of Romania (Barsana, Maramures County). The X-ray studies pointed out the presence of clinoptilolite as the main mineralogical phase (about 68%). The thermal analysis allowed evaluating the limiting temperature for the thermal stability, which agreed with literature reports for zeolites with SIO2/A1203 ratio of around 5.12, as it also resulted from our experiments. The acid treatment allowed elaborating an integrated technology for the use of volcanic tuff as an adsorbent material. Moreover, the resulting acid solution could be used in wastewater treatment.
01-P-10 - Heulandite group zeolites from the Paleogene flesh water lake Blateshnitza Graben, Southwest Bulgaria Z. Milakovska (a), E. Djourova (b) and R. Tzankarska (a)
a Geological Institute, Bulg. Academy of Sciences, Sofia, [email protected], Bulgaria b Faculty of Geology and Geography, Sofia University, djourova@gea, uni-sofia.bg, Bulgaria The Blateshnitza Graben is a continental fresh water lake basin filled with polymictic conglomerates, breccia-conglomerates and strongly subordinated sandstones. In the lowest volcaniclastic bed (---29 m depth), found in the upper part of the Zemen bore core (central part of the graben), heulandite group zeolites and probably ferrierite were identified by optical microscopy, SEM, XRD and DTA. Judging from the thermal stability, the main zeolite is heulandite, but the chemical data suggest that it should be considered as clinoptilolite. The features of the geological position and the environment of deposition suggest a zeolite genesis in an open hydrologic system.
01-P-11 - Isodimorphism of templates in zeolites. New crystal chemistry of analcime and its analogues V.V. Bakakin
Institute of Inorganic Chemistry, Russian Academy of Sciences, 630090, Novosibirsk, Russia A mechanism and reasons of an isomorphism of zeolite templates with numerically varying atoms are considered. The additional extraframework sites in the ANA type structures are separated and used. A simple graph of template nets is proposed and new algorithms of structural formulas are given. The notion of "template units" (TU) is brought forward. A set of TU that are involved in the formation of ANA compounds is determined. Examples of the actual combinations of these TU are given along with a summary of the corrected formulas and typical illustrations. A new interpretation of experimental data is given for 15 compounds and isomorphous series. Practically all inconsistencies in published data are eliminated.
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01-P-12- Evaluation of clinoptilolite tuffs from Russia as ion exchangers using NH4 ions I.V. Komarova, N.K. Galkina, V.A. Nikashina, B.G. Anfilov and K.I. Sheptovetzkaya
Vernadsky Institute of Geochemistry and Analytical Chemistry Russian Academy of Sciences (RAS), Kosygin str., 19, Moscow ,fax (095) 938 2054) e-mail [email protected] Russia This investigation resulted in the creation of the database of the equilibrium and kinetic characteristics of the zeolite tuffs using dynamic breakthrough curve. The computercontrolled system was developed in order to obtain experimental breakthrough curves, to carry out their mathematical treatment and to calculate necessary characteristics. The effective equilibrium and kinetic coefficients of some Russian clinoptilolite-containing tuffs from different deposits for the sorption of ammonium-ions were evaluated using this method, the data base was created. The chemical composition, the content of clinoptilolite in tuffs and total cation-exchange capacity of tuffs have been also included in the data base.
01-P-13 - Mineralogy, chemistry and ion-exchange properties of the zeolitized tufts from the Sheinovets caldera, E Rhodopes (South Bulgaria) R. Ivanova (a), Y. Yanev (a), Tz. Iliev (a), E. Koleva (a), T. Popova (b) and N. Popov (c)
(a)Geological Institute, Acad G. Bonchev St., 1113 Sofia, Bulgaria, [email protected] fo)Niproruda AD, 205 Stamboliiski Blvd., 1309 Sofia, Bulgaria (c)Institute of Cryobiology and Lyophilization, 65 Cherni Vrah Blvd., 1407 Sofia, Bulgaria Zeolitized tuffs from the Eastern Rhodopes Paleogene volcanic area have been studied. Namordenite and Ca-clinoptilolite are the main products of the acid glass alteration. Erionite, analcime and stilbite are also identified. Opal and adularia are most abundant at the base of tuff succession. Zeolite content increases upward; mordenite is prevailing in the middle and clinoptilolite in the topmost levels of the studied section. Compared with flesh perlite zeolitized tuffs are depleted in Na20, Y, Rb, Ba and Mn and enriched in CaO and Sr. C.E.C. coefficient ranges from 60.66 to 94.53 meq/100g. Low-temperature hydrothermal solutions, heated by the initially hot pyroclastic material are the inferred cause of the zeolite formation.
01-P-14 - Synthesis of titanium, niobium, and tantalum silicalite-1 by microwave heating of the mixed oxide xerogei precursors W.S. Ahn *a, K.Y. Kim a, M.H. Kim b and Y.S. Uh b
aSchool of Chemical Science and Engineering, Inha University, Inchon, Korea 402-751 whasahn@inha, ac. kr bMaterials Science and Technology Division, Korea Institute of Science and Technology, P. O. Box 131, Cheongryang, Seoul, Korea 130-650 Titanium (TS-1), niobium (NbS-1), and tantalum silicalite-1 (TaS-1) with MFI structure were synthesized by microwave heating of the TPAOH impregnated xerogels which were prepared by sol-gel process. Highly crystalline products were obtained in 30 min to 2 h with yields over 90%. The metallosilicates showed high catalytic performances in Beckmann rearrangement of cyclohexanone oxime to caprolactam.
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01-P-15 - Different silver states stabilized in natural clinoptilolites N. Bogdanchikova (a), B. Concepcion Rosabal (b), V. Petranovskii (a), M. Avalos-Borja (a) and G. Rodriguez-Fuentes (b)
a Centro de Ciencias de la Materia Condensada, UNAM, Ensenada, Mexico, [email protected] b Universidad de La Habana, La Habana, Cuba, [email protected] A set of samples prepared by introducing Ag into natural clinoptilolite were studied. Ag + cations, Agn and Agnm+ neutral and positively charged clusters, subcolloidal and large Ag particles were found in the prepared samples. It was revealed that variation of reduction temperature from 293 to 873 K allows to vary their contribution. All samples show a significant microbicide action against Escherichia coli strain bacteria and tumed out to be stable in air for more than 3 months. The natural clinoptilolite samples with Ag clusters and particles of different sizes is expected to be active in processes where a slow release of Ag + cation with olygodynamic properties is necessary.
01-P-16 - Physical-chemical and adsorptive properties of A r m e n i a natural zeolites F. Grigoryan, A. Hambartsumyan, H. Haroyan and A. Karapetyan State Engineering University of Armenia, Yerevan, e-mail." [email protected] The present research is devoted to the study of the physical-chemical properties of natural zeolites from Armenia. The adsorption of H2, O2, Ar, N2, CO2, SO2 on natural mordenite from Shirak deposit as well as the adsorption of Ar, N2, 802 and Xe on Shirak mordenite treated by hydrochloric acid have been studied by volumetric method. The kinetics of O2, Ar and N2 adsorption on natural mordenite have been studied. The isosteric heats of adsorption for H2, O2, Ar, N2, CH4, CO2, SO2, Xe have been measured by chromatographic method. The portion of quadropole interaction has been determined.
01-P-17 - The sorption equilibria in natural z e o l i t e - aqueous solutions systems J. Peri6 a, M. Trgo a and S. Cerjan-Stefanovi6 b ~Faculty of Chemical Technology, jperic@ktf-split, hr, mtrgo@ktf-split, hr~ Split, Croatia bFaculty of Chemical Engineering and Technology, Zagreb, Croatia Equilibrium properties of the hydrolysis and ion exchange process have been examined for natural and pre-treated zeolite-clinoptilolite by measuring the concentration of exchangeable . . . . N a+, K +, Ca2 + and Mg 2 + ions with time in the liquid phase. The analysis of the relation of concentrations of ionic species leaving the zeolite and those entering the zeolite structure (H+, Zn2+) has found to be a non-stoichiometric process.The established non-stoichiometry of the overall mass transfer process through the outer and inner surface of zeolite particles is due to the strength of the bond of exchangeable ions in the structure, as a phenomenon of sorption. The sorption takes place on characteristic locations on the zeolite particle surface, which has been confirmed by SEM images and EDX analysis.
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0 5 - Synthesis of New Materials (Tuesday) 05-P-06 - Synthesis and structures of GIS, A B W and G M E beryllophosphate molecular sieves from amine solutions H. Zhang (a), M. Chen(b), Z. Shi (c), Y. Zhou (a), Xin Xu (a) and D. Zhao (a)*
a Department of Chemistry; b Analysis and Measurement Center, Fudan University, Shanghai, 200433," c Department of Chemistry, Jilin University, Changchun, 130023, P. R. China. * dyzhao@_fudan,edu. cn. Several pure phase beryllophosphate molecular sieves with the topology similar to the gmelinite, gismondine and ABW frameworks have been successfully synthesized with the concentrated amines such as triethylene tetramine, piperazine, and pyridine as the structuredirecting agents. BePO4-GME is the first example of an open framework with the gmelinite topology in the phosphate system.
05-P-07 - Microporous gallosilicate TNU materials and their implications for the synthesis of low-silica molecular sieves W.C. Paik a, M.A. Camblor b and S.B. Hong *a
aDepartment of Chemical Technology, Taejon National University of Technology, Taejon 305-719, Korea; blndustrias Quimicas del Ebro, 50057 Zaragoza, Spain Hydrothermal syntheses of a series of gallosilicate molecular sieves, denoted TNU-n (Taejon National University Number n, where n = 1-7) are presented. The introduction of Ga into silicate frameworks was found to be a viable route to the discovery of novel low-silica zeolite structures. Among the materials prepared here, TNU-3 and TNU-4 with the NAT topology are characterized as members of a family of materials in which the two end members have random and non-random distributions of Si and Ga atoms over the available T-sites in the framework, respectively.
05-P-08 - Synthesis and characterization of novel nickel phosphates from non-aqueous systems Yunling Liu, L. Zhang, P. Zhang, Y. Zou and W. Pang*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, P R. China. E-mail. [email protected] Three novel organically templated nickel phosphates, NiPO4-n (n=l-3) have been prepared under solvothermal conditions using ethylenediamine as a structure directing agent. It is found that the use of solvothermal techniques and the involvement of fluoride ions are very essential to the outcome of the novel nickel phosphates. The products were characterized by powder X-ray diffraction, IR spectroscopy, SEM, TGA-DTA, ICP and elemental analysis and single crystal structure characterization. NiPO4-2 is a layered compound with 12-ring layers, NiPO4-3 is a new fluorinated nickel phosphate with a chain structure.
245
05-P-09 - Synthesis, characterization and properties of an anionic aluminophosphate molecular sieve with BrSnsted acidity W. Yan(a), J. Yu(a), R. Xu(a)*, Y. Han(a), K. Sugiyama(b) and O. Terasaki(c)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, [email protected], People's Republic of China b Department of Earth and Planetary Science, University of Tokyo, Tokyo113-0033, Japan c CREST, Japan Science and Technology Corporation, Tohoku University, Sendai, Japan An anionic aluminophosphate molecular sieve [AlzPI3052][(CH2)6N4H3] (denoted A1POCJB 1) with Br6nsted acidity upon removal of the template has been solvothermally prepared. It is constructed from alternation of Al-centered polyhedra (A104 and AIOs) and P-centered PO4 tetrahedra via vertex oxygens to form a negatively charged open-framework. The adsorption, ion-exchange and acidity properties are further characterized.
05-P-10 - Synthesis and characterization of an open-framework aluminophosphate [AIP206(OH)2][H30] containing propeller-like chiral motifs W. Yan, J. Yu, Z. Shi and R. Xu*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, rrxu@mail./lu.edu.cn, People's Republic of China A new open-framework aluminophosphate [A1P206(OH)2][H30] (denoted A1PO-CJ4) containing propeller-like chiral motifs with both A and A configurations has been prepared at the presence of 2-aminopyridine in a solvent of 2-BuOH. Single-crystal structural analysis gives that it crystallizes in the triclinic space group P-l, with a=7.1127(2)A, b=8.6729(2)A, c=9.220(3)A, a=65.108(2)~176176 and Z=3. A1PO-CJ4 is further characterized by X-ray powder diffraction, ICP, TG, and NMR analyses.
05-P-II - Synthesis and characterization manganese phosphate with GIS topology
of an aluminum-substituted
H.-M. Yuan, Y.-S. Jiang, W. Chen, J.-S. Chen* and R. Xu
Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, [email protected], edu. cn, Changchun, P. R. China An aluminum-substituted manganese phosphate (A1MnPO-GIS) containing tetrahedrallycoordinated Mn 2§ ions has been synthesized by using ethylene glycol as the predominant solvent and ethanolamine as the structure-directing agent under a solvothermal condition. It has been revealed that the material is analogousz§ to. zeolite glsmondine." The successful synthesis of A1MnPO-GIS suggests that the Mn -dominant aluminum-manganese phosphates with a different zeolite structure can be obtained by variation of template and reaction conditions.
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05-P-12 - Synthesis and characterisation of novel microporous framework cerium and europium silicates D. Ananias (a), P. Ferreira (a), A. Ferreira (a), J. Rocha (a), J.P. Rainho (a,b), C.M. Morais (a) and L.D. Carlos (b)
a Department of Chemistry, University of Aveiro, 3810 Aveiro, Portugal b Department of Physics, University of Aveiro, 3810 Aveiro, Portugal The synthesis, structural characterization and luminescence spectroscopy studies of AV-5 and AV-9 (Aveiro microporous solids no. 5 and 9), the first examples of microporous framework cerium(III) and europium(III) silicates (Na4KzX2Si16038"10H20, X = Eu, Ce) are reported. Both materials display interesting photoluminescence properties and present potential for applications in optoelectronics. This work illustrates the possibility of combining in a given framework silicate microporosity and optical activity.
05-P-13 - Novel microporous framework stannosilicates Z. Lin and J. Rocha
Department of Chemistry, University of Aveiro, 3810 Aveiro, [email protected], Portugal Reactions in the R20 - S n O 2 - S i O 2 - H 2 0 (R = Na, K) system have been studied under mild hydrothermal conditions (170 - 230 ~ Synthesis variables such as time, temperature and the HzO/Sn, Si/Sn, K/Sn, K/Na and OH/Sn ratios have been investigated. Two novel microporous framework stannosilicates, AV-6 and AV-7, have been prepared. These materials possess corner-sharing [SnO6] octahedra and [SiO4] tetrahedra forming threedimensional frameworks, with no Sn-O-Sn-O chains, stable up to ca. 700 and 450 ~ respectively. After calcination of AV-6 and AV-7 for 5 hours at 900 and 1000 ~ respectively, a new phase (AV-11) forms. At higher temperature, AV-11 converts to a wadeite type structure. The materials have been characterized by SEM, powder XRD, 298i and l l9Sn MAS NMR and TGA.
0 5 - P - 1 4 - Magadiite intercalated MCM-22 M. Munsignatti, A.J.S. Mascarenhas, A.L.S. Marques and H.O. Pastore*
Grupo de Peneiras Moleculares Micro- e Mesoporosas, Instituto de Quimica, Universidade Estadual de Campinas, CP 6154, CEP 13083-970, Campinas, SP, Brasil. E-mail adress: lolly@iqm, unicamp, br MCM-22 precursor samples were prepared with magadiite. The layered assembly was intercalated with CTABr/TPAOH, sonicated, Soxhlet extracted and calcined. The material was characterized by XRD, pore analysis, SEM, FTIR, elemental analysis and DTG. The samples obtained appear to be the result of magadiite layers intercalated at least partially, between MCM-22 layers.
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05-P-15- Synthesis of aluminum phosphite microporous materials N. Li and S. Xiang*
Department of Chemistry, Nankai University, Tianjin 300071, P R. China E-mail." shxiang@public, lpt. tj. cn A series of aluminum phosphite and phosphite-phosphate molecular sieves were synthesized by using P (III) (phosphorous acid) partly or completely replaced P (V) (phosphoric acid) as the source of phosphorus materials. DPA (di-n-propylamine), TEA (triethylamine) and CHA (cyclohexylamine) were used as the template respectively. SEM photographs showed the shapes of these crystalline inorganic solid. It was very interesting that a kind of aluminum phosphite NKX-4 can be synthesized with or without template.
0 5 - P - 1 6 - Synthesis, characterization and structural aspects of novel microporous indium L.M. King, J. Gisselquist, S.C. Koster, D.S. Bern, R.W. Broach, S.G. Song and R.L. Bedard
UOP-LLC, 25 East Algonquin Road, Des Plaines, Illinois This paper reports the synthesis and characterization of a new family of indium silicate microporous materials, designated InSi-n. The InSi-n phases have been synthesized with 11 novel framework topologies and contain In/Si ratios of 0.25-1. Most InSi-n phases are stable to calcination to at least 500 ~ and show adsorption behavior that is zeolitic in character. Ion exchange behavior similar to zeolites has also been observed in InSi-n materials. Preliminary structural details include a crystal structure determination of a new topology with 8-ring channels and HREM evidence for large pores in members of the InSi-n family.
05-P-17 - Synthesis and characterization of the silicoaluminophosphate SAPO-47 L. Xu, Z. Liu, P. Tian, Y. Wei, C. Sun and Shinian Li Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P. O. Box 110, Dalian 116023, [email protected], China Synthesis of a novel small-pore SAPO-47 molecular sieve was described. The effects of the templates and silica concentration in the synthesis gel on the crystallinity and phase purity of SAPO-47 were studied. The results show that pure SAPO-47 could be obtained in a wide range of SIO2/A1203 using sec-butylamine, methylbutylamine or iso-butylamine as templating agent. It is evident that the strength and the amount of the acid sites are related closely to the silicon content and distribution in the framework. SAPO-47 molecular sieve catalyst with expected acidity could be obtained by controlling the SIO2/A1203 in the initial gel.
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05-P-18 - Synthesis, characterization MAPSO-56 molecular sieves
and
catalysis
of SAPO-56
and
P. Tian, Z. Liu, L. Xu and C. Sun
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, [email protected],ac.cn, China Using N,N,N',N'-tetramethyl-l,6-hexandiammine as organic template, SAPO-56 and its metal-containing silicoaluminophosphates (M=Co, Mn and Zr) were synthesized hydrothermally. The synthesis phase diagram and crystallization kinetics of SAPO-56 were obtained. The synthesis regulation of pure MAPSO-56 molecular sieves was also investigated. The samples were characterized by XRD, SEM, TG-DTA and MAS NMR. SAPO-56 and MAPSO-56 were studied with respect to their catalytic behaviors in the methanol-to-olefins conversion and the oxidation of alkane, respectively.
05-P-19 - Synthesis and structural characterization of a novel microporous zeolitic type aluminium phosphate C. Sassoyea, S. Girard a, C. Mellot-Draznieks a, T. Loiseau a, C. Hugeunard b, F.Taulelle b and G. F6reya alnstitut Lavoisier (IREM), UMR CNRS 8637, Universit6 de Versailles, 45, avenue des EtatsUnis, Versailles, France - [email protected]; bRMN et Chimie du Solide, UMR ULPBrtiker-CNRS 7510, Universit6 Louis Pasteur, Strasbourg, France This contribution deals with the hydrothermal synthesis and the structure characterization of a new microporous aluminium phosphate AI4(PO4)4(OH), NC4HI0, labelled MIL-34. The openframework is built up from interconnected tunnels bounded by 8-membered rings. The cyclobutylamine molecules which are used as structure-directing agent are found at the intersection of the 8-ring channels.
05-P-20 - Hydrothermai synthesis and crystal structures of two novel open frameworks: (enH2)3[Co3W4P402s] and (dapH2)3[Co3W4P402s] B. Yan*, Y. Xu, N.K. Goh and L.S. Chia
Natural Science, Nanyang Technological University, Singapore [email protected] Two novel microporous cobalt tungsten(VI) phosphates, (enH2)3[Co3W4P4028] 1 and (dapH2)3[Co3W4P402s] 2, were hydrothermally synthesized and characterized by thermogravimetry, elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The structure of solid 1 comprises corner sharing PO4, CoO4 tetrahedra and WO6, CoO6 octahedra linked through bridging oxygen atoms. The pore system contains 7- and 8membered rings. The structure of solid 2 has the same topology as structure 1.
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07 - N e w M e s o p o r o u s Molecular Sieves (Tuesday) 07-P-06 - Vanadosilicate: cubic m e s o p o r o u s molecular sieve M. Chatterjee, T. Iwasaki, Y. Onodera, H. Hayashi, T. Ebina and T. Nagase
Inorganic Materials Section, Tohoku National Industrial Research Institute, Nigatake 4-2-1, Miyagino-ku, Sendai 983-8551, Japan Mesoporous vanadosilicate molecular sieves with MCM-48 structure and atomic Si/V ratio 30-200 have been synthesized using vanadyl sulphate as the source of vanadium. The product was characterized using X-ray diffraction (XRD), N2 adsorption analysis, transmision electron microscopy (TEM), electron spin resonance (ESR), Fourier-transform Infrared (FTIR), Diffuse reflectance UV-visible spectroscopy (UV-vis) and 5~V solid state NMR. A noticeable decrease in unit cell parameters and main pore diameter was observed. Thus, a strong interaction between vanadium and mesoporous wall can be suggested.
07-P-07 - Synthesis and characterization of m e s o p o r o u s Cu-silica spheres via a novel c o - a s s e m b l e route P. Zhang, N. Bai, X. Meng and W. Pang* Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun, 130023, P R. China Email." wqpang@mail./lu.edu.cn Transparent mm-sized mesoporous Cu-silica spheres have been synthesized successfully through the introduction of Cu(II)-APTMOS complex into the reaction mixture. The products are characterized by powder XRD, N2 adsorption, TEM, SEM, ESR, and ICP techniques. The pore structure of Cu-silica spheres is disordered. The Cu II ions in Cu-silica spheres are in typical six-coordinated environment and cannot be exchanged by other metal ions. The primary experimental results show that the mesoporous Cu-silica spheres exhibit high catalytic activities in the hydroxylation of phenol under the presentation of H202
07-P-08Synthesis and characterization of m e s o s t r u c t u r e d alumina prepared in the presence of d o d e c y l p h o s p h a t e L. Sicard a, B. Lebeau a, C. Marichal a, J. Patarin a and F. Kolenda b a Laboratoire de Matdriaux Mindraux, Ecole Nationale Supdrieure de Chimie de Mulhouse, B.Lebeau@univ-mulhouse fr, France. b Institut Frangais du Pdtrole, Vernaison, France. The present study focuses on the mechanisms of formation of two dodecylphosphate (DDP) mesostructured alumina synthesized at pH = 5 and 8 respectively. For the material synthesized under acidic conditions, NMR experiments seem to indicate the presence of AIO-P bonds. The material would be of aluminophosphate type rather than a pure alumina. The sample synthesized under basic conditions contains large amounts of sodium. In this case, the interactions between the surfactant S and the alumina framework I are weak and the mechanism of formation would be of SM+I ~ type, where M is the counterion (Na+).
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07-P-09 - Synthesis and characterizations of mesoporous zirconia-based oxide composites J. Zhaoa; D. Wua; Y.-H. Suna*; Zh. Zhangb; H. Zhang b and D. Zhao b a Institute of Coal Chemistry, C.A.S., [email protected], P R. China b Department of Chemistry, Fudan University, Shanghai, 200433, P. R. China The thermal stability of mesoporous zirconia with tetragonal wall was greatly improved via incorporation with SiO2 and A1203. FT-IR and NMR indicated that there were chemical interactions between SiO2 (A1203) with zirconia, which strengthened tetragonal framework, thereby improving the thermal stability of crystalline mesoporous zirconia.
0 7 - P - 1 0 - Preparation and catalytic property of FeL/Y composite by a new method B. Fan, W. Fan and R. Li* Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P.R. China. E-mail: rfli~tvut, edu. cn A new method, viz. the recrystallization of MCM-41 impregnated metal complex in the synthesis system of zeolite Y, has been developed to immobilize the guest complex in zeolite host. In this way, a series of FeL/Y composites (with L=phenanthroline (phen), 8-quinolinol (Qx), salicylic acid (SA)) have been prepared. The as-prepared materials are characterized by XRD, FTIR, UV-vis, TG-DTA and ICP techniques. Furthermore, their catalytic properties in the reaction of cyclohexane oxidation were also investigated. It was shown that this method made it possible to immobilize different metal complexes, including the cationic, the anionic and the neutral. In addition, the content of metal complex can be controlled by varying its amount impregnated on MCM-41.
07-P-II - Mesoporous zirconia" an anionic surfactant inorganic composite, precursor of a tridimensional porous material G. Pacheco and J.J. Fripiat Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin, Milwaukee, P.O.Box 413, Milwaukee, WI, USA. Mesoporous zirconias obtained by hydrolyzing zirconium isopropoxide at low pH (.3) in presence of alkyl straight-chain surfactant are disordered composite materials that develop high surface areas and mesoporosity. They differ essentially from mesoporous materials obtained by templating since their surface area and porosity are available in the presence of the surfactant. Another building mechanism, accounting for this difference is suggested.
251
07-P-12 - Synthesis of micelle templated TiO2 mesophases by a sol-gel approach: effect of the surfactant removal D.P. Serrano, G. Calleja, R. Sanz and P. Pizarro ESCET, Universidad Rey Juan Carlos. C~ Tulip~n s/n , 28933 M6stoles, Madrid, Spain. e-mail: dserrano@escet, urjc. es Mesoporous TiO2 has been synthesized in the presence of a non-ionic surfactant by N~ ~ assembly, using a Ti alkoxide as Ti source. The porous structure partially collapses upon calcination. However, this fact can be avoided by extraction of the surfactant with boiling acid/ethanol mixtures. Thus, TiO2 samples with surfaces areas up to 470 m2/g and pore sizes in the range 2-6 nm have been obtained. DR UV-Vis spectra of the as-synthesized samples show the presence of Ti species with both tetrahedral and octahedral coordinations, which resemble that of anatase powder.
0 7 - P - 1 3 - Preparation and characterization of iron oxide nanoparticles in the channels of MCM-41 C.M. Yang and K.J. Chao Department of Chemistry, National Tsinghua University, Hsinchu 300, Taiwan e-mail." kjchao@mx, nthu. edu. tw Ferrocene was incorporated into the templating micelles of synthetic siliceous MCM-41, and found to affect the morphology and structure of MCM-41. Ferrocene was oxidized to tetrahedrally coordinated oxide isolatedly grafted on the pore wall after calcination at 600~ in oxygen, and transformed to oxide nanoparticles in MCM-41 by further heating at 800~ under vacuum, characterized by TEM, in-situ XAS and EPR measurements.
07-P-14 - The evaluation of iron chromophore concentrations from iron containing MCM-41 C. Nenu, R. Ganea, R Birjega, Gr. Pop and M. Pitu ZECASIN S.A., Spl. Independentei 202, Bucharest, [email protected], Romania This study aims to provide a fast method to evaluate the iron incorporation degree in the walls of iron-containing mesoporous materials. Both Fe-MCM-41 systems and Fe+AI-MCM-41 systems were prepared with C~6TMABr as surfactant, in hydrothermal conditions. The colour of the iron containing MCM-41 samples is determined just by coloured chromophores and, taking into account that the intratetrahedral FeO4 is not, it can be established a connection between colour, respectively luminescence (L), and the concentration of iron chromophores, in fact the extraframework species. An incorporation degree of iron into MCM-41 walls and additionally, an extraframework iron percent would be evaluated by this method.
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07-P-15 - Synthesis and characterization of the mesoporous material of single crystal particles B. Lee (a), J.N. Kondo (a), D. Lu (b) and K. Domen (a, b) a Chemical Resources Laboratory, Tokyo Institute of Technology, [email protected], Japan b Core Research for Evolutional Science and Technology, JST, Japan Mesoporous structure was constructed in single crystal particles of niobium and tantalum mixed oxide 9 TEM and electron diffraction indicated single crystal phase with the mean pore size of 10 nm. The crystallized mesoporous material showed mechanical and hydrothermal stability.
07-P-16 - Stabilization of uniformly sized and dispersed copper particles in new Cu-Zn-A! mesoporous catalysts S. Valangea, b, J. Barrault b, A. Derouault b and Z. Gabelica a ENSCMu, GSEC, 3, Rue A. Werner, F-68093, Mulhouse, [email protected],
France bLACCO, UMR CNRS 6503, ESIP, 40, Av. du Recteur Pineau, F-86022 Poitiers, France A series of binary Cu-A1 and ternary Cu-Zn-A1 surfactant assisted mesoporous precursors prepared through direct synthesis yielded after calcination and reduction, both Cu ~ and Cu20 clusters of variable size, well dispersed on the mesoporous alumina substrate. These materials proved particularly selective in the hydrogenation of the carbonyl group of cinnamaldehyde, due to the presence of a large number of nanometer sized Cu20 particles that stay uniformly dispersed and in strong interaction with the A1 mesoporous walls. In the ternary Cu-Zn-A1 mesoporous systems, ZnO exerts a major influence on the catalytic performance of such catalysts. Experimental evidence of a CuzO/ZnO synergetic interaction is given.
07-P-17 - A direct synthesis route to the mesoporous silicate SBA-2 bearing thiol groups 9
a*
I. Diaz a, F. Mohino a, J. P6rez-Panente , E. Sastre a, P.A. Wright b and W. Zhou b
Instituto de Catdlisis y Petroleoquimica (CSIC), Cantoblanco, 28049 Madrid, Spain. b School of Chemistry, The University of St. Andrews, Fife KY16 9ST, Scotland, U.K. The mesoporous silicate SBA-2 has been prepared in the presence of mercaptopropyltriethoxysilane (MPTES) and gemini surfactants in basic medium. The thiol-containing units are incorporated quantitatively and at a loading of 10%MPTES a high degree of structural order is retained, as shown by XRD and TEM. Attempts to remove the templates by extraction were successful, and it is possible to oxidize thiol to sulfonic acid groups. The oxidized material containing -SO3H groups has been tested in the esterification of fatty acids.the esterification of glycerol with oleic acid. Factors affecting the catalytic performance of these materials are discussed.
253
07-P-18- Template synthesis and characterization of nanoporous alumina with narrow pore size distribution from inorganic salts H.Y. Zhul, p. Cool 2, G.Q. Lu I and E.F. Vansant 2 i Department of Chemical Engineering, The University of Queensland, Australia, hyzhu@cheque, uq. edu. au 2 Laboratory of Adsorption and Catalysis, University of Antwerp (UIA), Belgium A polyethylene oxide (PEO) surfactant and an aqueous solution of inorganic aluminum salt were used to prepare activated aluminas with narrow pore size distributions (PSD). The condensation of the aluminum hydrolysate species around the micelles of the surfactant was induced by urea. Mesoporous structure of alumina formed as the surfactant was removed. It is also found that the function of the PEO surfactant depends on synthesis route. Highly porous alumina was obtained by another process, from the same PEO surfactant and an inorganic salt of aluminium. The proposed synthesis approach is of importance to the preparation of activated alumina with various pore structures in industrial practice.
0 7 - P - 1 9 - Preparation and characterization of copper oxide modified MCM-41 molecular sieves C. Minchev a, R. K~hn b, T. Tsoncheva a, M. Dimitrov a and M. FrOba b'c
aInstitute of Organic Chemistry, BAS, 1113 Sofia, Bulgaria bInstitute of Inorganic and Applied Chemistry, University of Hamburg, Germany cInstitute of Inorganic Chemistry, University of Erlangen-Nuremberg, Germany Using three different preparation methods copper oxide modified MCM-41 silica and A1MCM-41 materials were obtained and characterized by various techniques (nitrogen physisorption, XRD and TPR-TGA) and methanol decomposition as a catalytic test reaction. At certain conditions of impregnation and drying at room temperature and under vacuum it was possible to form highly dispersed CuO nanoparticles incorporated almost exclusively within the mesoporous host structure. These particles could be reduced with H2 at considerably lower temperatures than the bulk CuO.
0 7 - P - 2 0 - Crystalline, m e s o p o r o u s N i O - Z r O 2 - b a s e d solid oxide fuel cell catalysts P. Ratnasamy,* D. Srinivas, H.S. Soni, A.J. Chandwadkar, H.S. Potdar, C.S. Gopinath and B.S. Rao
National Chemical Laboratory, Pune 411 008, India, [email protected] Nickel-supported, yttria-stabilized zirconia, alumina-yttria-stabilized zirconia and ceriastabilized zirconia samples were prepared as fuel cell anode catalysts by three different methods. The structural, textural and electronic properties of the materials were investigated by XRD, N2 adsorption, chemisorption, XPS, DRS and EPR techniques. These materials have cubic fluorite structure stable upto 973K and high specific surface area and average mesopore size. Cerium promotes the reduction of Ni 2* ions. Samples prepared by hydrothermal synthesis in the presence of structure-directing templates, like quaternary ammonium ions have a high surface concentration of nickel, high catalytic activity and a slower deactivation in the steam reforming of n-decane.
254
07-P-21 - Application of the A A S B U method to the prediction of inorganic structures built exclusively of sodalite cages S. Girard (a), P. Pullumbi (b), C. Mellot-Draznieks (a) and G. F6rey (a) a Institut Lavoisier (IREM), Universit6 de Versailles, France, [email protected], mellot@chimie, uvsq.fr b Air Liquide, Centre de Recherche Claude-Delorme, Jouy-en-Josas, France. The AASBU computational method is used here with the aim of producing a library of inorganic zeolitic structures based on sodalite cages exclusively. The calculations are based on a combination of a simulated annealing procedure and "cost function" minimizations that enforce connections between individual sodalite cages. The assumptions for each simulation run are the space group and the number of sodalite cages per unit-cell. The simulations successfully generated the known SOD or LTA frameworks as well as hypothetical frameworks. Lattice energy calculations of these hypothetical frameworks in their pure silicate form, SiO2, suggest that they have stabilities similar to existing zeolites.
07-P-22 - Novel synthesis of nanoporous carbons using colloidal templates S.B. Yoon, I.S. Shin and J.-S. Yu* Department of Chemistry, Hannam University, Taejon, 306-791, Chungnam, Korea [email protected]; fax: 82-42-629-7446 Ordered porous carbons were synthesized by replication of colloidal templates made from 30
- 100 nm diameter silica spheres and removal of the silica templates using aqueous HF. To create the templates, the monodisperse particles were pressed into pellets and then sintered slightly at their points of contact. The silica template were filled with carbon precursor solution of divinylbenzene (DVB) and a free radical initiator, azobisisobutyronitrile (AIBN). Polymerization and carbonization of the precursor solution and subsequent dissolution of the silica templates leave a polycrystalline network of carbon with interconnected uniform pores. The degree of order of the silica template is faithfully reproduced in the carbon replicas.
07-P-23 - Synthesis and characterization of mesoporous cerium silicate analogues of M C M - 4 1 type molecular sieves S. Laha, P. Mukherjee and R. Kumar Catalysis Division, National Chemical Laboratory, Pune 411 008, INDIA (Fax. +91-20-5893761/5893355; E-mail: [email protected]) Cerium-containing MCM-41 mesoporous materials were synthesized using different methods. X-ray diffraction pattem, N2 adsorption and different spectroscopic analyses of the samples reveal that organized mesoporous MCM-41 materials were prepared. The presence of Ce is confirmed by EDX analysis. High BET surface area (494-1415 m2gl ) and typical XRD pattern of MCM-41 type hexagonal structure of these materials indicate the presence of hexagonal mesopores in the samples. The presence of a strong absorption centered at ca. 290 nm and an absence of ca. 400 nm absorption in the UV-Vis spectra, indicate the presence of tetra coordinated cerium in the Ce-MCM-41 samples.
255
07-P-24 - Synthesis of m e s o p o r o u s materials using filtrate of alkali t r e a t m e n t of M F I zeolite M. Ogura, E. Kikuchi and M. Matsukata
Department of Applied Chemistry, Waseda University, [email protected], Japan. Synthesis of M41S mesoporous materials was attempted using MFI type zeolite as sources of silica and aluminum, that is, dissolution of MFI zeolite in an alkaline solution and successive precipitation of dissolved aluminosilicate species with a surfactant, cethyltrimethylammonium bromide (CTAB). Pure phase of M41S was obtained when the filtrate of alkali-treated slurry was mixed with CTAB and crystallized at 293K. The M41S materials obtained in this method showed a catalytic activity originated from Br~nsted acid site of the parent MFI zeolite. This method enables us to obtain a new type of mesoporous materials, which have both characteristics of zeolitic and mesoporous materials: a strong Bronsted acidity and mesopores with a uniform size.
256
1 5 - Modelling and Theoritical Studies A (Tuesday) 15-P-06 - A reactivity index study to choose the best template for zeolite synthesis A. Chatterjee and T. Iwasaki
Inorganic Materials Section, Tohoku National Industrial Research Institute, 4-2-1 Nigatake, Miyagino-ku, Sendai 983-8551, JAPAN. Email: [email protected], Fax.'81-22-236-6839 The activity of different representative templating molecules along with zeolite framework is investigated using a range of reactivity indexes using density functional theory (DFT). From the values of local softness and the charge on the hydrogen atom of the bridging hydroxyl, resulted from the presence of aluminum in the framework, it is observed that the acidities of the aluminum containing zeolite type model systems, are dependent on several characteristics which are of importance within the framework of hard and soft acids and bases (HSAB) principle. We investigated the local softness of the interacting templates, to compare their affinity with the zeolite framework cluster models. A priori rule is formulated to choose the best template for a particular zeolite (e.g. ZSM-5) synthesis.
15-P-07- Effects of ion-exchanged alkali metal cations On the photolysis of alkyl ketones included within ZSM-5 zeolite cavities: A study of ab-initio molecular orbital calculations H. Yamashita*, S. Takada, M. Nishimura, H. Bessho and M. Anpo*
Osaka Prefecture University, yamashita@chem, osakafu-u.ac.ip, Japan Effects of ion-exchanged alkali metal cations on the adsorption and the photolysis (Norrish type I and type II reactions) of 2-pentanone included within the alkali metal cation-exchanged ZSM-5 zeolite have been investigated by experimental and theoretical approaches. The yields of the photolysis decreased and the ratio of the type I/ type II reactions increased, respectively, by changing the ion-exchanged cations from Cs + to Li +. The observed IR spectra of the adsorbed ketones and the ab initio molecular orbital calculations of this host-guest system indicate that the type I and type II reactions proceed from the staggered and eclipsed conformations of 2-pentanone, respectively, and that the smaller cation has the stronger electrostatic interaction between ketone and promotes the type I reaction of ketone efficiently.
15-P-08 - Encapsulated guest atoms within the basic beta cage of sodalitic zeolite. A theoretical ab-initio study N.U. Zhanpeisov and M. Anpo
Department of Applied Chemistry, Osaka Prefecture University, 1-I Gakuen-cho, Osaka 5998531, Japan, nurbost,n@ok. chem. osakafu-u.ac.jp Ab-initio quantum chemical calculations at the HF/3-21G* level of theory were applied to consider the nature of the active sites of sodalite [3-cage of the LTA type zeolite and faujasite structures. Especially, the nature of sodium, potassium and silicon atoms encapsulated within the sodalitic [3-cage, and their structural and molecular parameters have been described. We have shown that up to four sodium and four potassium atoms as well as five silicon atoms could be encapsulated within the sodalite 13-cage. The unique properties of these nano-size materials relate directly to the encapsulated guest atom containing fragments stabilized within the sodalite [3-cage of the LTA type zeolite or faujasite structures.
257 15-P-09n-Hexane aromatization over Pt-alkaline zeolites: ab-initio calculations on the influence of the exchanged cations and zeolite type (L, 13 and Y) on electronic properties of Pt S.B. Waghmode, P. Bharathi, R. Vetrivel and S. Sivasanker*
Catalysis Division, National Chemical Laboratory, Pune 411 008, lndia; [email protected] Zeolites L, 13 and Y exchanged with different ions (H, Li, Na, K, Cs and Ba) and loaded with 0.6 wt% Pt have been tested for n-hexane aromatization activity. Activity of the catalysts depends on the exchanged ion and on the zeolite support. Ab-initio calculations (restricted Hartree-Fock) made, using representative cluster models of the three zeolites and a Pt5 cluster, to determine the average charge of Pt supported on different ion-exchanged zeolites reveal an increase in the electronic charge on Pt with the basicity of the exchanged ion. Relationship between the average charge on Pt and benzene yields over the catalysts is reported.
15-P-10-
A theoretical study of adsorption of carbon monoxide on Ag-
ZSM-5 zeolite S. Jungsuttiwong, P. Khongpracha, T.N. Truong, and J. Limtrakul
Laboratory for Computational & Applied Chemistry, Chemistry Department, Kasetsart University, Bangkok 10900, Thailand," e-mail: [email protected] Calculated results obtained from the embedded cluster method at B3LYP/6-31G(d,p) yielded a metal-oxygen distance of 2.300 (2.30+0.03) A for the Ag+-ZSM-5; the value in the parenthesis is taken from the experimental results. The Madelung potential, represented by sets of point charges surrounding the quantum cluster causes metal-oxygen distances to be elongated by 0.05-0.07 A which make all predicted results agree very well with the observations. The calculated high frequency of C-O stretching in the Ag+-ZSM-5 complex is on account of the larger Ag+-C bond (2.07.3,) as compared to the Cu+-C bond (1.85 A). This large distance can to some extent prevent the contribution of the 7t-back bonding in silver carbonyl complexes.
15-P-I 1 - A theoretical~spectroscopic study of the coordination of transition metal ions in zeolites A. Delabie (a), M.H. Groothaert (b), R.A. Schoonheydt (b) and K. Pierloot (a)
a Laboratory of Quantum Chemistry, University of Leuven, Celestijnenlaan 200 F, B-3001 Heverlee-Leuven, Belgium," b Center for Surface Chemistry and Catalysis, University of Leuven, K. Mercierlaan 92, B-3001 Heverlee-Leuven, Belgium. Knowledge about the coordination of transition metal ions in zeolites is important for the understanding of the catalytic properties of these materials. ESR and DRS have provided spectroscopic signatures for Cu in different zeohtes. In this work, high-level theoretical calculations (DFT, CASPT2) are used for the assignment of the spectroscopic signals to specific coordination modes. The general features of the Cu2+-zeolite interaction are summarized in three rules, which are then illustrated by the siting of Cu 2+ in mordenite. 9
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1 5 - P - 1 2 - Ab-initio study of the adsorption and reactions of hydrocarbons in mordenite T. Demuth(a), L. Benco(a), J. Hafner(a), H. Toulhoat(b), and F. Hutschka(c)
alnstitut fi~r Materialphysik, Universiti~t Wien, Sensengasse 8/12, 1090 Wien,Austria, [email protected] blnstitut Franfais du Pdtrole, F-92852 RueilMalmaison, France CTotalFina Raffinage Marketing, B.P. 27, F-76700 Harfleur, France We have studied the interaction of n-alkanes, n-alkenes, and benzene with acid mordenite using density functional theory. The adsorption strength is correlated to the local structural distortion of the zeolite framework, especially of the acid site. Only for strong adsorption, the molecule is slightly deformed as in the case of benzene adsorption. The analysis of the differential indicates pronounced polarization effects on both the acid site and the adsorbed molecule. The H/D exchange reaction of benzene has been analyzed by calculating the reaction energy diagram.
15-P-13 - Properties of Cu 2+ and Cu + cations in MFI framework: DFT and IR studies E. Broclawik a, J. Datka b, B. Gil b and P. Kozyra b
alnstitute of Catalysis, Polish Academy of Sciences, [email protected], ul. Niezapominajek 8, 30-239 Cracow, Poland bFaculty of Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Cracow, Poland In this paper we present quantum chemical calculations for the extended model of ZSM-5 framework based on seven T sites in two fused 5T rings cut off the MFI structure. This model is large enough to be a good host for Cu 2+ and Cu + and for adsorbed NO molecule 9 Coordination of the copper cation depends strongly on its oxidation state. Divalent copper prefers planar square coordination in the centre of 6T ring while Cu + forms three bonds with framework oxygens in a five-ring. NO molecule is strongly bonded by both Cu 2+ and Cu + but it becomes significantly activated only after sorption on Cu +. Combined calculations and IR data confirm migration of copper after oxidation/reduction and NO adsorption. Cu+ZSM-5 activates NO very strong and is very active in deNOx.
15-P-14 - Nonempirical (ab-initio) and semiempirical calculations of the elementary fragments of zeolites. Permeability of ring zeolite fragments A.V. Gabdrakipov, L.D. Volkova, N.A. Zakarina and V.Z. Gabdrakipov*
Institute of Organic Catalysis and Electrochemistry, Ministry of education and Science. Kunaev Street 142, Almaty, 480100, Kazakhstan. With the purpose of determining the permeability of rings S6R in zeolites, calculations at the Hartree-Fock (ab-initio) and semiempirical PM3 levels have been performed for models including H , L1 , N a , Rb ions and H, He, Ar, Kr atoms. The semlempmcal calculations were achieved for models with H and Na ions and H20, NH3, CH4, C2H6, C3H8 molecules. The geometry of a fragment of zeolite, i.e. a cubic octahedron Si24036(OH)24, was optimized with PM3. Then the fragment Si6018 was extracted and the free valency oxygen atoms in S6R were saturated with hydrogen atoms 9The ab-initio calculations have shown the presence of a potential hole at the center of the fragment S6R. Barrier values have been evaluated in the case of atoms He, Ar, Kr (ab-initio) and simple molecules (PM3). 9
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15-P-15 - Modelling light alkane transformation over HZSM-5 zeolite x. Wang a' b, F. Lemos a, and F. Ram6a Ribeiro a
aCentro de Engenharia Biol6gica e Quimica, Departamento de Engenharia Quimica, Instituto Superior T6cnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. blnstitute of Industrial Catalyst, Dalian University of Technology, 158 Zhongshan Road, 116012 Dalian, China. Light alkane conversion over HZSM-5 zeolite occurs usually by a protolytic monomolecular mechanism. In the present study we will analyse a set of experimental results obtained for the transformation of light alkanes over HZSM-5, at various temperatures (350 ~ - 500 ~ and compare these results with quantum chemical calculations for these transformations over model acid sites. It was concluded that similar transition states were formed for the cracking of C-C bonds in different alkanes, always with relatively high activation energies.
1 5 - P - 1 6 - Activity-acidity relationship in Y zeolite: an experimental and quantum-chemical study X. Wang a' b, M.A.N.D.A. Lemos a, F. Lemos a, C. Costa a, and F. Ram6a Ribeiro a
~Centro de Engenharia Biol6gica e Quimica, Departamento de Engenharia Quimica, Instituto Superior T6cnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. blnstitute of Industrial Catalyst, Dalian University of Technology, 158 Zhongshan Road, 116012 Dalian, China. The aim of the present paper is to show that there is a clear relation between the catalytic activity and the acidity for acid catalysis using Y zeolites and that this relationship has theoretical support through quantum chemical calculations on model acid sites. The study presented is centred on the transformation of ethene and propene over acidic Y and USY zeolites.
15-P-17 - DFT study of structure changes in hydrated AIPO4-n : the case of AlPO4-34 G. Poulet, A. Tuel and P. Sautet
Institut de Recherches sur la Catalyse, [email protected], France. The structural relaxation of calcined A1PO4-34 and the geometry distortion of the compound upon adsorption of water have been studied by DFT plane-wave calculations on periodic models. A good correlation was found between experimental and optimized structures for both the dehydrated and fully hydrated compounds. In the latter, the 3D-channel system is filled with water molecules, some of them being coordinated to framework aluminum, and forming a strong H-bond network. Energetic and geometric calculations reveal that one specific non-framework water molecule is less strongly bonded and can reversibly desorb at room temperature, in agreement with the existence of a partially hydrated phase observed experimentally by X-ray diffraction.
260
15-P-18 - A mechanistic exploration of alkene epoxidation mediated by H202 within porous titanosilicate catalysts C.M. Barker(a), N. Kaltsoyannis(b) and C.R.A. Catlow(a)
aThe Royal Institution of Great Britain, London, UK, [email protected]. bUniversity College London, UK. Density Functional Theory has been employed to examine the geometry, coordination, stability, energetics of formation and oxygen-donating mechanism of Ti-peroxo complexes in peroxide doped Ti substituted molecular sieve epoxidation catalysts. Through a combination of DFT calculations and Ti EXAFS of a tert-butyl hydroperoxide exposed surface grafted Ti?MCM41 catalyst we have determined that the active species in titanosilicate catalysts are 6 coordinate. Furthermore, we propose that both Ti(q2-OOR) and five membered ring Ti(TI2OOR) complexes are energetically stable and are likely to be present in peroxide/Ti substituted molecular sieve systems.
15-P-19 - Transition-state shape-selectivity insights from a Fukui function overlap method L.A. Clark a and R.Q. Snurr
Department of Chemical Engineering and Center for Catalysis and Surface Science, Northwestern University Evanston, IL 60208 ~email."[email protected] The theory and implementation of a novel computational method capable of looking at large transition-state shape-selective systems is outlined. It is then applied to the alkylation reaction of toluene in the gas phase as well as in zeolites MFI, MOR and BEA. Alkylating agents from the series methyl, ethyl, iso-propyl and tert-butyl are employed to investigate the size and shape effects of the confinement.
15-P-20 - A DFT study of the isomerization reactions of aromatics catalyzed by acidic zeolites X. Rozanska, R.A. van Santen, F. Hutschka a and J. Hafner b
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands aTotalFinaElf, Centre Europ6en de Recherche et Technique, D6partement Chimie des Proc6d6s, B.P. 27, 76700 Harfleur, France blnstitut fiir Materialphysik, Universitdt Wien, Sensengasse 8, A-1090 Wien, Austria A DFT study of the isomerization reactions of toluene catalyzed by acidic zeolite is reported. Monomolecular isomerization reactions have been considered and analyzed. The different reaction pathways have been discussed in detail. The uses of periodical structure calculations as well as small cluster approach method calculations allow to analyze the effect of zeolite electrostatic contributions and steric constraints on reactivity.
261
15-P-21 - Ab-initio investigation of non-framework aluminum species in zeolites D. Lopes Bhering a, C.J.A. Mota a and A. Ramirez-Solis b
~Instituto de Quimica, Universidade Federal do Rio de Janeiro, Rio de Janeiro, 21949-900, Rio de Janeiro, Brazil. (cmota@iq. ufrj. br) 6Faculdad de Ciencias, Universidad Aut6noma del Estado de Morelos, Cuernavaca, Morelos, 6221 O, MOxico Structure and chemical shifts of non-framework aluminum (NFA) were studied by ab-initio methods. A T6 cluster (T=Si, A1) was used to simulate the zeolite structure. The NFA are preferentially coordinated to the oxygen atoms of the framework AIO4. For 3- and 4coordinated species, the predicted "A1 NMR results show downfield chemical shifts (7095ppm) related to the experimentally observed ones (0-60ppm). This suggests that some of the species do not exist or that they may be coordinated with water. For 5-coordinated NFA the calculated chemical shifts was between the octahedral and tetrahedral value (45-55 ppm).
15-P-22 - A DFT study of the cracking reaction of thiophene activated by zeotype catalysts: role of the basic Lewis site X. Rozanska, R.A. van Santen and F. Hutschka a
Schuit Institute of Catalysis, Laboratory of Inorganic Chemistry and Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands ~TotalFinaElf, Centre Europ~en de Recherche et Technique, D6partement Chimie des Proc~d6s, B.P. 27, 76700 Harfleur, France A DFT study of the cracking reaction of thiophene catalyzed by zeolite is reported. The use of different zeotype catalysts (viz. acidic, metal-exchanged and methoxy) has been shown to successfully induce this reaction. It appears that the thiophene cracking reaction is catalyzed by a basic Lewis site and that acid Bronsted site has only a limited influence on the reaction.
15-P-23 - Modelling transition metal cations in zeolites: how do they interact with the framework? D. Berthomieu a, A. Goursot a, J-M. Duc6r6 a, G. Delahay a, B. Coq a and A. Martinez b
~LMCCCO UMR-CNRS 5618, ENSCM, 8, rue de l'Ecole Normale, 34296 Montpellier Cedex 5- France- [email protected] blnstituto de Investigaciones in Materiales, Circuito Exterior s/n, C. U. Apdo. Postal 70-360, C. P. 04510, Mdxico, D.F. Mdxico Density Functional Theory has been used to study model clusters of zeolites Y and 13 containing Fe(II), Co(II) and Cu(II) TM cations. The calculations yield a charge of around + 1 on TM whatever are their coordination, the size of the cluster and the A1 distribution. This result is obtained only with TM and most probably comes from a charge transfer from the zeolite to TM. We show that the TM-zeolite system behaves as a supermolecule and that the zeolite is able to keep or release electrons when reactive molecules are incoming.
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15-P-24 - Theoretical prediction of IR spectra of guest molecules in zeolites: the stretching frequency of CO adsorbed at various cationic sites in Z S M - 5 T.A. Wesolowski (a), A. Goursot (b) and J. Weber (a) (a) Department of Physical Chemistry, University of Geneva, 30 quai Ernest Ansermet, 1211 Genbve 4, Switzerland (a) UMR 5618 CNRS, Ecole de Chimie, 8 rue de l'Ecole Normale, 34296, Montpellier, C~dex 5, France The influence of the microscopic environment of the cationic site in ZSM-5 as well as the long-range effects on the CO stretching frequency and on its binding energy has been studied using a DFT-based methodology. Our results show that the choice of the A1 site does not affect significantly the calculated shifts whereas the binding energies display more variations. The calculated frequency shifts agree with experiment within few cm l.
15-P-25 - D e v e l o p m e n t of a tight-binding treatment for zeolites M. Elstner a, A. Goursot b, Z. Hajnal c, T. Heine d and J. Weber d Department of Molecular Biophysics, D-69120 Heidelberg; b UMR 5618, Ecole de Chimie, 8 rue de l'Ecole Normale, F-34296 Montpellier,'~University of Paderborn, Department of Theoretical Physics, D-33098 Paderborn, d University of Geneva, Department of Physical Chemistry, CH-1211 Geneva 4," [email protected] Density-Functional based Tight-Binding (DFTB) calculations of two types of zeolites (MAZ, BEA) are presented. For these systems, a unit-cell was fully optimized using periodic boundary conditions in the G point approximation and these results are compared with cluster approximations, where unit-cell dangling bonds are saturated with H. For mazzite, a small cluster model including the two crystallographic sites are also compared with full DensityFunctional theory (DFT) results. The method shows good agreement with experimental X-ray data and DFT values. It is extended to treat zeolites containing aluminum.
15-P- 26 - 1-D growth of selenium wires in silicalite-1 zeolite C. Bichara a and R.J.-M. Pellenq b a CRMC2- CNRS, Campus de Luminy, Case 913, 13288, Marseille, [email protected]./k. b CRMD - CNRS et Universit6 d'OrHans, 1bis rue de la F6rollerie, OrHans, 45071. A computer simulation of the adsorption of Selenium in silicalite is presented. The Se-Se interactions are calculated in a quantum mechanical tight-binding approach. The Se-silicalite interactions are assumed to be of Van der Waals type. The adsorption/desorption isotherms are characteristic of a mechanism where adsorbate-adsorbate interactions are much larger than the adsorbate/matrix interactions: they exhibit a large hysteresis loop which tends to disappear as temperature increases. At sufficiently low temperature, the adsorption branch shows some sub-steps which magnitude and position depend on the simulation box size. These sub-steps are followed by brutal jumps corresponding to filling of the remaining porosity. All these features are rather uncommon for adsorption in a microporous system.
263 1 5 - P - 2 7 - Cumulative coordinates for approximations of atomic multipole moments in cationic forms of aluminosilicates A.V. Larin (a) and D.P. Vercauteren (b)
a Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, B-234, 119899, Russia; b Laboratoire de Physico-Chimie Informatique, Facultds Universitaires Notre Dame de la Paix, Rue de Bruxelles 61, B-5000 Namur, Belgium Atomic multipole moments (MMs) are calculated for three LiABW, NaNAT, and BaEDI aluminosilicates with the periodic Hartree-Fock CRYSTAL95 code. The positions of the cations with and without included water molecules were optimised. Approximate functions for the MMs which can be used for further calculations of the electrostatic potential in an arbitrary zeolite are proposed in terms of the charges and geometry of their neighbour atoms.
15-P-28- Computer simulations of water in zeolites C. Bussaia b, R. Haberlandt a, S. Hannongbuai b and S. Jost a
a,b University Leipzig, Institutefor Theoretical Physics, Leipzig, Germany, b Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, Thailand The topic of water in zeolites is viewed from different points. On the one hand, Hatree-Fock and MP2 quantum chemical calculations have been performed to investigated water-silicalite interaction as well as the energy barrier and water orientations during diffusion in the silicalite. The results indicate how water molecules move and turn during movement through the center of the silicalite pore. The energy barriers for water molecules to enter the pore and to diffuse from one channel to the other have been examined. The water molecules enter and leave the pores preferably by pointing its d~pole vector towards the center of the cavity. On the other hand we present molecular dynamics simulations with a well established empirical water model in the chabazite. Both water molecule and zeolite lattice are modelled flexible. The diffusion and the configuration of the water molecules inside the zeolite are examined.
264
16- Modelling and Theoriticai Studies B (Tuesday) 16-P-06- Location of triethylmethylammonium ions in MFI by combining molecular modeling and X-ray diffraction R. Millini EniTecnologie S.p.A, 20097 San Donato Milanese (MI-Italy) - [email protected] A Quench Dynamics protocol (a combination of high temperature Molecular Dynamics and Energy Minimization techniques) is used for predicting the location of triethylmethylammonium (TEMA) cations in zeolite MFI.' Rietveld refinement of the high-resolution synchrotron X-ray diffraction data confirms these predictions. The TEMA cations are located at the channels intersections in two different conformations with two ethyl groups located in the linear channel.
16-P-07 - A hypothetical zeolite structure MCRI6: topological design and template choice B. Li (a), P. Sun (b), Q. Jin (a) and D. Ding (a)
a Department of Physics; Nankai University, Tianjin 300071, [email protected], China b The State Key Laboratory of Functional Polymer Materials for Adsorption and Separation, Institute of Polymer Chemistry," Nankai University, Tianjin, China The topological structure of a novel zeolite, named MCR16, with cylindrical channels spanning 16-membered rings, is constructed by means of the sigma transformation of the known zeolite mordenite. The consistent molecular mechanics force field is employed, and the minimized energy structure is obtained. The calculated heat of formation of MCR16 is comparable to that of mordenite. Six organic molecules that might be used as template in synthesizing this novel structure are discussed based on the calculations of the non-bonding interaction energies between the organic molecules and MCR16 frameworks.
16-P-08 - Computational analysis of the shape-selective isopropylation o! biphenyl over large pore zeolites J. Joffre (a), D. Mravec (b) and P. Moreau (a)
a Ecole Nationale Sup&ieure de Chimie de Montpellier, joffre@cit, enscm.fr, France. b Organic Technology, Slovak University of Technology, Bratislava, Slovak Republic. Computational analysis of molecular dimensions and diffusion energies of the various monoand di-isopropylbiphenyl isomers has been performed, using molecular mechanics and quantum mechanics methods. The 4,4'-diisopropylbiphenyl has the lowest kinetic diameter and diffusion energy, which is in agreement with the experimental results regarding the high para-selectivity observed in the isopropylation reaction of biphenyl over H-mordenites. The above calculations in the biphenyl series show that modelling analysis appears to be useful to understand the experimental results, and confirms other computational results in the field of the shape-selective alkylation of naphthalene.
265
16-P-09 - De novo simulation and spectroscopic study of iron speciation in ZSM-5 and CIT-5 P.-P.H.J.M. Knops-Gerrits l* and W.A. Goddard III2
t CMAT, D@artement de Chimie, Univ. Cath. de Louvain, Belgium, [email protected] : MSC, Beckman Institute (139-74), California Inst. of Technology, USA wag@wag, caltech, edu The introduction of iron in the lattice of zeolite topologies such as MFI and CFI is performed via direct synthesis and post-synthetic modification. Dinuclear iron clusters in appropriate zeolites realize oxidation of methane into methanol at room temperature after NzO activation. Both mono and dinuclear iron coordination and lattice coordination is treated with theory and experiment. In FeCIT-5 and Fe-ZSM5 are made by "over-exchange" via sublimation of iron salts in Al-zeolites. When extra-framework iron oxides are made in zeolites, the extraframework iron oxide clusters can be anchored to zeolites.
1 6 - P - 1 0 - Exact statistical mechanical treatment of a lattice model of hydrocarbon adsorption on zeolites G. Manos (a), L.J. Dunne (b,c), Z. Du (c) and M.F Chaplin (c)
Department of Chemical Engineering, University College London, Torrington Place, [email protected], London, WCIE 7JE, UK School of Chemistry, University of Sussex, Brighton, UK. c School of Applied Science, South Bank University, London SE10AA, UK. In this paper, we present an exact calculation of the statistical mechanics of a lattice model of hydrocarbon adsorption in the quasi one-dimensional pores of zeolites, based on a matrix method that utilises the Constant Pressure partition. The model is tested on benzene adsorption, where it reproduces experimentally observed steps in isotherms. The model has been extended also to linear alkanes where it reproduces very accurately experimental adsorption isotherms as well as Monte-Carlo simulation results of ethane.
16-P-I 1 - Computational studies of the structure of Na- and H-Mordenite A.E. Gray, A. O'Brien and D.W. Lewis
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University College London, U.K., [email protected], [email protected] A combined Monte Carlo and energy minimisation method has been developed to model zeolitic materials with low and medium Si/A1 and with a variety of extra-framework species. We present results for Na- and H-Mordenites with Si/A1 of 5 and 11. The A1 and cation distributions obtained are in reasonably good agreement with experimental studies. Furthermore, our calculated vibrational spectra are in excellent agreement with experiment, which has allowed us to re-interpret the de-convolution and assignment of the various acid sites.
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16-P-12 - M o n t e Carlo simulation of isobutane in silicalite D. Paschek and R. Krishna
University of Amsterdam, paschek@its, chem. uva.nl, The Netherlands Recent experimental work on transport diffusion of alkanes in zeolite Silicalite [B. Millot et al., J. Phys. Chem. B, 103 (1999) 1096; B. Millot et al., Micropor. Mesopor. Mater., 38 (2000) 85] indicates a possible change of the diffusion mechanism of branched components when approaching higher loadings. Therefore, we report kinetic Monte Carlo (KMC) simulations of diffusion of isobutane adsorbed in Silicalite. By using configurational-biased Monte Carlo (CBMC) simulations we get evidence for the presence of repulsive interactions between molecules adsorbed at adjacent intersection and straight channel sites. Our KMC simulations reveal that even weak repulsive interactions have a rather strong influence on the diffusivities at higher loadings and therefore could serve as a possible explanation for the experimentally observed behavior.
16-P-13 - Characterisation of hypothetical zeolite f r a m e w o r k s M.D. Foster (a), R.G. Bell (a) and J. Klinowski (b)
a DFRL, Royal Institution of GB, London, UK, [email protected], [email protected]. b Dept. of Chemistry, Univ. Cambridge, UK A series of hypothetical zeolite structures has been evaluated on the basis of calculated lattice energies and structural properties. The structures were those generated by Delgado and coworkers, using recent advances in tiling theory. Over 900 structures are currently under evaluation, from which results are presented of the 157 uninodal structures based on a quasisimple tiling unit, which include all 18 presently known uninodal zeolite structures. Treating each structure as a silica polymorph, we have calculated relative lattice energies, framework densities and coordination sequences. An automated procedure uses these quantities and correlations between them, to make an initial selection of likely candidate zeolite structures.
16-P-14 - Cation mobility and the sorption of chloroform in zeolite NaY: a molecular d y n a m i c s study N.A. Ramsahye and R.G. Bell
DFRL, Royal Institution of Great Britain, London, UK;[email protected] Molecular dynamics simulations at temperatures of 270 K, 330 K and 390 K have been carried out in order to address the question of cation migration upon chloroform sorption in zeolite NaY. The results show that the cations located in different sites exhibit different types of mobility. These may be summarised as follows: 1. SII cations migrate towards the centre of the supercage upon sorption, due to interactions with the polar sorbate molecules. 2. SI' cations migrate from the sodalite cage into the supercage to fill vacant SII sites. 3. The SI cations are able to migrate across double six rings and sodalite cages in order to fill another vacant SI' site. SI' cations can also migrate to fill another vacant SI' site.
267
1 6 - P - 1 5 - Computational studies of the calcination of fluorinated gallophosphates" exploration of their template-free calcined forms S. Girard (a), J.D. Gale (b), C. Mellot-Draznieks (a) and G. F6rey (a)
Institut Lavoisier (IREM), Universitd de Versailles, France, [email protected], mellot@chimie, uvsq.fr b Department of Chemistry, Imperial College of Science Technology and Medecine, UK. The stability of four fluorinated templated gallophosphates upon calcination is anticipated using lattice energy minimizations and appropriate interatomic potentials, starting from their as-synthesized structures. A careful analysis of the frameworks and energetics of the four predicted calcined structures helped us to consider their viability. Three of them have zeotype frameworks and their lattice energies suggest the stability of their as-synthesized forms upon calcination. One of the latter compounds corresponds to its experimentally calcined structure, thus validating the calculations. The last predicted calcined compound shows unrealistic structural feature suggesting the high unstability of its as-synthesized form upon calcination.
16-P-16 - Molecular simulation studies on the effectiveness of template type on TS-I crystal morphology H. Zhou, H. He and Z. Jing
Research Institute of Petroleum Processing, China Petrochemical Corporation, P.O. Box 914, Beijing 100083, [email protected], China. Molecular simulation approaches were used to investigate the effectiveness of template type on TS-1 crystal morphology. Calculations indicated that docking of hexane diamine on surfaces of TS-1 crystal strongly changes crystal size and morphology. It is also found that hexane diamine can pack together with TPA in TS-1 structure to play an important template effect. Simulation results consistent well with experimental results.
16-P-17- A molecular dynamic approach on the selective conformationai change of ethylene glycol in sodalite cage M. Sato
Department of Chemistry, Gunma University. Kiryu, Gunma376, Japan In order to investigate the conformational stability of ethylene glycol molecule in the sodalite cage, a molecular dynamic simulation is performed on the force field MM+ as well as semiempirical PM3. As the result, the gauche(+) conformer is confirmed to be more stable than the gauche(-) one in the sodalite cage.
268 1 6 - P - 1 8 - T h e mutual influence of dynamic processes acting in different
time scales S. Fritzsche a, R. Haberlandt a, A. Schfiring a and M. Wolfsberg b
a University Leipzig, Institute for Theoretical Physics, Leipzig, Germany," b Institute for Surface and Interface Science, University of California, Irvine, USA. Diffusion and relaxation processes of different nonspherical guest molecules in zeolites are examined by MD simulations with rigid and flexible lattice and molecules. Interrelations between such processes are studied by different tools, e.g. correlation functions. The results show that there exsist cases where a strong mutual influence can be found and others in which there is only small influence.
1 6 - P - 1 9 - Lattice-dynamical calculations for zeolites of natrolite group S.V. Goryainov (a) and M.B. Smirnov (b)
a Institute of Mineralogy and Petrography, Novosibirsk-90, Russia, [email protected] b Institute for Silicate Chemistry, St. Petersburg-155, Russia, [email protected] Lattice-dynamical calculations for unit cells of natrolite and edingtonite were performed. It was shown that strongest Raman bands of natrolite at 534 cm z and edingtonite at 530 cm 1 are related to breathing modes of 4-membered rings. Assignment of vibrational spectra of used zeolites, presented here for symmetric modes of natrolite, may provide a base for interpretation of vibrations in other zeolites. Calculated natrolite crystal structure exhibits instability at about 5.5 GPa, which corresponds to amorphization observed at pressure range of 4-7 GPa.
16-P-20 - Kinetic modelling of the dynamic interaction between NO and N20 over Cu-ZSM5 R. Pirone a, P. Ciambelli b, A. Di Benedetto a, B. Palella c and G. Russo a
~lstituto di Ricerche sulla Combustione, CNR, Napoli, Italy- [email protected]; bDipartimento di Ingegneria Chimica e Alimentare, Universit~ di Salerno, Fisciano, Italy," ~Dipartimento di Ingegneria Chimica, Universit~ di Napoli "Federico II", Napoli, Italy. Spontaneous and isothermal oscillations of N20 decomposition rate have been observed in Cu-ZSM5. In the presence of NO, oscillations desappear and the overall reaction rate significantly increases. A kinetic model has been developed to describe this phenomenom proposing a redox mechanism which describes the interaction between NO and N20 over CuZSM5.
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1 9 - Diffusion: Fundamental Approach (Tuesday) 19-P-06 - Modeling of sulfur dioxide breakthrough curves from ternary wet mixtures on MOR type zeolite M. Mello a, M. Eid a, S. Ho(,evarb and U. Lavren6i~-Stangarb
aDepartment of Chemical Engineering, University of New Brunswick, P.O. Box 4400, Fredericton, N.B., Canada E3B 5A3 ([email protected]); bNational Institute of Chemistry, Laboratory of Catalysis and Reaction Engineering, Hajdrihova 19, 61115 Ljublj'ana, Slovenia The adsorption of SO2 from temary mixtures with water and CO2 on high silica MOR zeolite was investigated using the breakthrough curve method. The breakthrough model was based on axially dispersed plug flow through the column, and mixture equilibrium was described by Langmuir 1 extended model. The solution was obtained by finite element collocation method using the commercial software gPROMS. Infra-red spectroscopic measurements gave further evidence that water was more strongly adsorbed than SO2, thus displacing it and causing rollup effect.
19-P-07- The diffusion and sorption dynamics of acetylene in zeolites G. Onyestydk (a), J. Valyon (a) and L.V.C. Rees (b)
a Institute of Chemistry, Chemical Research Center, Hungarian Academy of Sciences valyon@cric, chemres, hu, Hungary b Department of Chemistry, University of Edinburgh, Edinburgh, United Kingdom Species formed from acetylene (Ay) adsorbed in zeolite Y, mordenite, beta and ZSM-5 have been studied by IR spectroscopy. The dynamics of Ay physisorption has been characterized by the frequency response method (FR). The rate of micropore diffusion governed the transport in Na-mordenite, while sorption was the rate limiting process step for all the Hzeolites. The equilibrium constants (Ka) of Ay sorption have been determined applying the Langmuir rate equation to describe the pressure dependence of the sorption time constants. The n-octane hydroconversion activity of Pt/H-zeolites was found to increase linearly with the Ka of Ay sorption on the H-zeolites.
19-P-08 -Transient uptake measurements using an oscillating microbalance: effect of acid leaching on the diffusivity of n-hexane in Pt/Hmordenite S. van Donk, A. Broersma, O.L.J. Gijzeman, J.H. Bitter and K.P. de Jong*
Department of Inorganic Chemistry and Catalysis, Debye Institute, Utrecht University, The Netherlands; *Corresponding author, e-mail: [email protected] Measurements performed in a tapered element oscillating microbalance (TEOM) reveal that diffusivities can be derived from uptake data monitored under full reaction conditions. In this way the effect of acid leaching on the diffusional behaviour of n-hexane in Pt/H-Mordenite is investigated. It is shown that acid leaching largely enhances the n-hexane uptake rate, but does not result in a net increase in the intracrystalline steady state diffusivity. It is concluded that the accelerated uptake after acid leaching merely arises from the shorter intracrystalline diffusion path resulting from the mesoporous structure.
270
19-P-09 - Use of 129Xe N M R spectroscopy to study gaseous hydrocarbon diffusion in a fixed bed of HZSM-5 zeolite M.-A. Springuel-Huet, P. N'Gokoli-Kekele, C. Mignot, J.-L. Bonardet and J. Fraissard Laboratoire SIEN-Chimie des Surfaces, Universitd P. et M. Curie, Paris, mas@ccr:/ussieu.:fr, France The diffusion of gaseous benzene and paraxylene during their adsorption in a fixed bed of HZSM-5 zeolite crystallite has been studied by 129Xe NMR of adsorbed xenon used as a probe. The equations of diffusion in the macropores and micropores have been analytically solved, giving the hydrocarbon concentration profiles against time in both types of pores and allowing the simulation of the 129Xe NMR spectra. The comparison of simulated and experimental spectra leads to the value of the intracrystallite diffusion coefficients which are in good agreement with the literature.
19-P-10 - Adsorption and diffusion of alkanes and their mixtures in silicalite studied with positron emission profiling technique A.O. Koriabkina, D. Schuring, A.M. de Jong and R.A. van Santen Schuit Institute of Catalysis, Technical University of Eindhoven, [email protected], The Netherlands With the TEX-PEP technique experiments on the diffusion and adsorption of mixture of nhexane/2-methylpentane in large silicalite-1 crystals have been performed. By modeling the experimental tracer exchange curves values of intracrystalline diffusion coefficient and adsorption constant were obtained. Slight preference for the adsorption of n-hexane was found. Diffusivity of n-hexane sharply decreases with increasing fraction of its isomer, since the last one occupies channel intersections thus blocking zeolite network.
271
2 4 - N e w Routes to H y d r o c a r b o n Activation (Tuesday) 24-P-06 - Study of coke and deactivation over H-Beta zeolite Z. Zhu, T. Ruan, Q. Chen, W. Chen and D. Kong
Shanghai Research Institute of Petrochemical Technology- China, [email protected] The nature of coke over H-Beta strongly relates to different types of reactions. The coking rate, in line with the deactivating rate during three reactions, increases in the following order: toluene disproportionation, n-heptane cracking, benzene alkylation. With the increase of HBeta Si/A1 ratio, the decrease of the coking rate becomes slower, because the effect of the acid site decrease on coking is compensated by the increase of the space available for coking from the secondary pores. But the decrease of deactivating rate keeps constant. The coking rate over H-Beta is higher than that over H-MOR. The deactivation rate of H-Beta is much lower than that of H-MOR since its three-dimensional interlining system without supercage is not as easy to be blocked as pseudo-unidimensional channels of H-MOR.
2 4 - P - 0 7 - Photoionization of N - a l k y i p h e n o t h i a z i n e s in transition-metal-ion modified m e s o p o r o u s silica S B A - 1 5 molecular sieves Z. Luana, b and L. Kevan a aDepartment of Chemistry, University of Houston, Houston, Texas 77204-5641 E-mail. KEVAN@ UH.EDU bphilip Morris, P.O. Box 26583, Richmond, VA 23261-6583 N-Alkylphenothiazines with variable alkyl chain lengths have been incorporated into mesoporous silica SBA-15 containing framework titanium or vanadium. Photoionization at room temperature forms stable alkylphenothiazine cation radicals (PCn +) which are monitored by electron spin resonance. The results reveal that the photoyield and stability of PCn + increase with increasing titanium and vanadium content suggesting that these ions serve as effective electron acceptors. The overall photoyield and stability of PCn + also increase with increasing alkyl chain length of the alkylphenothiazines.
24-P-08 - Potential use of A I M C M - 4 1 for activation of metallocene catalyst T. Sano, T. Niimi, T. Miyazaki, S. Tsubaki, Y. Oumi and T. Uozumi School of Materials Science, Japan Advanced Institute of Science and Technology, Tatsunokuchi, Ishikawa 923-1292, Japan 9E-mail " [email protected] Polymerizations of ethylene and propylene were conducted with racethylene(bisindenyl)zirconium dichloride(rac-Et(Ind)2ZrClz) with triisobutylaluminium(Al(i-C4H9)3) using A1MCM-41 evacuated at various temperatures. A linear relationship between the polymer yield and the number of Lewis acid sites on the A1MCM-41 was observed. Lewis acid sites on the A1MCM-41 are able to activate effectively the metallocene compound, resulting in the formation of active species for olefin polymerization.
272
24-P-09 - Activation of butanes with olefins' carbenium cations over zeolite catalysts S.E. Dolinsky(a) and V.A. Plakhotnik (b) a New Catalytic Technologies Ltd., [email protected], Moscow, Russia b Institute of Organic chemistry RAS, Moscow, Russia Most publications concerning alkylate manufacturing (as component of blended gasoline) from light hydrocarbons assume application of "new types" of zeolites - BETA, MCM, EMT. However "old types" of zeolites have not yet completely discovered their potential. We developed modified technique for producing bi-functional zeolite X based catalysts with superacid centers of narrow acidity distribution (various analytical data to prove this fact are given). Besides, such zeolites are employed for the alkylation of n-butane and ethylene yielding isobutane/butylenes. Catalyst lifetime and content of isooctanes in alkylate increase significantly (up to 5 times and up to 95 % respectively).
24-P-10 - Immobilization and mobilization of surface species during transformation of ethylene over H Z S M - 5 catalysts A. Zikdnovd (a), M. Ko6ifik (a), M. Derewifiski (b), P. Sarv (c), J. Dubsk)~ (a), P. Hudec(d) and A. Smie~kovfi (d) a* J. Heyrovs~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, 182 23 Prague 8, kocirik@l'h-inst.cas.cz, Czech Republic, b* Institute of Catalysis and Surface Chemistry,, Niezapominajek l, 30-239 Cracow, Poland, c*Institute of Chemical Physics and Biophysics, Estonian Acad. of Sciences Tallin, Estonia d* Slovak University of Technology, Radlinsk~ho 9, SK 81237 Bratislava, Slovak Republic Amount of ethylene immobilized in HZSM-5 catalysts was estimated from sorption and reaction dynamics as a function of reactor temperature. Space accessible in loaded crystals was measured using water sorption at 298 K.
24-P-11 - Zeolite-L as support of Fe microcrystals for the F i s c h e r - T r o p s c h synthesis M.V. Cagnoli, N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, A.A. Yeramian and S.G. Marchetti CINDECA, Fac. Cs. Exactas, Fac. Ingenieria, UN.L.P., CIC, CONICET., mavic@quimica, unlp. edu. ar Calle 47 N ~ 257 (1900) La Plata, Argentina. Zeolite-L in potassic form (Fe/ZLK) was used as support of iron species to be used as catalyst in the Fischer-Tropsch reaction. The oxide precursor was reduced using two different programmes. Thermal programme reduction (TPR), X-Ray Diffraction (XRD), Specific Surface area (BET), "In-situ" M6ssbauer Spectroscopy (MS) between room temperature and 15K, H2 chemisorption and Volumetric Oxidation (VO) were used to characterize the solids. Using a slow reduction treatment, it was possible to maintain a high quantity of Fe ~ microcrystals inside the pore structure, leading to a higher activity to low molecular weight paraffin.
273
24-P-12 - Nb- and Ti-containing silica-based mesoporous molecular sieves as catalysts for photocatalytic oxidation of methane J. Xin a, X. Chen b, J. Suo a, Xia. Zhang a, L. Yan a and Shuben Li a
aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou,, [email protected], cn, China bCollege of Chemistry and Chemical Engineering, Guangxi University, Nanning, China Nb- and Ti-containing silica-based mesoporous molecular sieves were used as catalysts for photocatalytic oxidation of methane. It is found that methanol was formed at 323 K and water pre-adsorbed samples exhibited higher catalytic activity than their pure metal oxides. By comparison with Nb-MCM-41, Ti-MCM-41 gave better methane conversion and methanol yield although traces of formaldehyde were observed over Nb-MCM-41 catalyst. Interestingly, OH radical was detected by the in-situ ESR spectroscopy using DMPO as trapper.
24-P-13 - Catalytic properties of micelle templated microporous and mesoporous materials for the conversion of low-density polYbethylene J. Aguado a, D.P. Serrano a, R. Van Grieken a, J.M. Escola a and E. Garagorri
aSuperior School of Exp. Sciences and Technology (ESCET), Rey Juan Carlos University, c~ Tulip{m s/n, 28933, M6stoles, Madrid, Spain, e-mail: [email protected] bChemical Engineering Department, Complutense University, Av. Complutense s/n, 28040, Madrid, Spain Both microporous and mesoporous micelle templated aluminosilicates have shown high catalytic activity for the LDPE craking. A1-SBA-15 materials have been used for the first time as higly effective catalyts for the conversion of polyolefins. The most active catalyts, according to their TOF values, were those with the highest Si/A1 atomic ratios (Si/AI> 150), which has been assigned mainly to a lower deactivation kinetic. For all the samples investigated, the main products were liquid hydrocarbons within the range C5-C 14 (-70%).
2 4 - P - 1 4 - Epoxidation of propylene in fixed bed reactor using supported titanium silicalite catalyst X.S. Wang, Gang Li, H.S. Yan and X.W. Guo
State Key Laboratory, Dalian University, Dalian, P. R. China (Fax." +86-411-3689065) Two molding methods were adopted to prepare the titanium silicalite catalyst used in a fixed bed reactor. One is the traditional extruding method in which strip TS-1 catalyst is obtained. The other is a new kind of molding method in which lamina TS-1 catalyst is made by spraying the powdery TS-1 on a small inert ball. The lamina TS-1 catalyst exhibits better performance in propylene epoxidation than the strip TS-1 catalyst.
274
2 4 - P - 1 5 - Acetylene and alkene oligomerization on ETS-10 having induced Bronsted acidity A. Zecchina a, C. Paz~ a, C. Otero Arefinb; G. Turnes Palominob; F.X. Llabr6s i Xamena b and S. Bordiga a
Dipartimento di Chirnica I.F.M., Univ. di Torino, Torino, Italy," b Departamento de Quimica, Univ. de las Islas Baleares, Palma de Mallorca, Spain
a
H-ETS-10, prepared by careful thermolysis of ammonium-exchanged ETS-10, was found to have significant Bronsted acidity as revealed by its ability to protonate adsorbed pyridine. Interaction of methyl-acetylene with the Bronsted acid sites of H-ETS-10 results in protonation, followed by formation of oligomeric species with carbocationic character. The n-delocalization of the positive charge of oligomers results in a characteristic spectroscopic response both in the IR and UV-Vis. Similarly, propylene was also found to undergo oligomerization on H-ETS-10.
24-P-16 - Isomerization of n-butane over small crystals of H-Beta and Pt-HBeta zeolite catalysts N. Kumar l, M. Vainio l, V. Nieminen I, R. Byggningsbacka l, L.-E. Lindfors I, T. Salmi I, D.Y. Murzin I and E. Laine 2
1Laboratory of Industrial Chemistry, Process Chemistry Group,/[bo Akademi University, Biskopsgatan 8, FIN-20500 Abo, Finland, Fax." 358 2 2154479 2Department of Physics, University of Turku, 20014 Turku, Finland Beta zeolites with average crystal sizes of 2 pm and 0.6 pm were synthesized and characterized using different techniques. The Pt-H-Beta and H-Beta catalysts were prepared using 0.6 ~tm crystals of Beta zeolite. The catalytic activities of the synthesized catalysts were investigated in the isomerization of n-butane to iso-butane. The influence of reaction temperature, catalyst pretreatment and carrier gas was investigated for the conversion of nbutane and selectivity to iso-butane. The Pt-H-Beta catalyst in presence of hydrogen as a carrier gas led to higher conversion of n-butane and selectivity to iso-butane than nitrogen.
24-P-17 - Ethylene oligomerization with nickel-containing NaX zeolite M.O. de Souza, F.M.T. Mendes, R.F. de Souza, J.H.Z. dos Santos, L. Caumo, V. Conz, F. Majolo and L.V. Barbosa.
Universidade Federal do Rio Grande do Sul- Instituto de Qufmica- Av. Bento Gongalves, 9500- 91501-970 Porto Alegre, Brazil-e-mail." [email protected]~s.br FAX" (51) 3191499 Nickel complex-containing zeolite materials Ni(MeCN)6(BF4)2/NaX and Ni(acac)2 have been prepared and characterized by X Ray photoelectron spectroscopy (XPS). These materials are catalytically active for ethylene dimerization and 1-butene isomerization. The supported systems show higher selectivity towards 1-butene formation compared with the homogeneous system. These features were attributed to a new nickel species formed in the supported systems.
275
2 4 - P - 1 8 - Studies of the methanol to hydrocarbons reaction using isotopic labelling. Mounting evidence for a hydrocarbon pool mechanism S. Kolboe
Department of Chemistry, University of Oslo, P.O. Box 1033, N0315 Oslo, Norway. Recent data, published and unpublished, provide strong evidence that the common views on the reaction mechanism of the MTH reaction are not tenable. The data rather point to ethene and propene formation from an adsorbate hydrocarbon pool, probably of aromatic nature. There are strong indications that the catalytic cycle is based on arenes that are continually methylated by methanol/dimethyl ether, and dealkylations leading to ethene, propene and most likely also isobutene via molecular rearrangements. Penta- and hexamethylbenzene appear prone to undergo this reaction. However, there is also clear evidence that higher alkenes, if present in substantial amount, may take part in the "classical" homologation system.
24-P-19- Formation and reactivity of alkoxy species through the reaction of alkylhalides with metal-exchanged zeolites R.J. Corr~a and C.J.A. Mota
Instituto de Quimica, Universidade Federal do Rio de Janeiro, Cidade Universit6ria CT Blco A, Ilha do Fund6o, Rio de Janeiro, 21949-900, Brazil. ([email protected]) The formation of alkoxy species on metal exchanged zeolites was observed upon exposure to 5 Torr of butylchlorides at ambient temperature. The reaction was followed by infrared spectroscopy and the reactivity of the alkoxy species toward proton elimination was also monitored.
24-P-20 - The use of ITQ-7 as catalyst for alkylation of isobutane with 2butene A. Corma, M.J. Diaz-Cabafias, C. Martinez and S. Valencia
Instituto de Tecnologia Quimica, UP V-CSIC, acorma@itq, upv. es, Spain. The catalytic behavior of an AI-ITQ-7 zeolite, with a three-dimensional system of large pore channels, has been evaluated for the liquid phase alkylation of isobutane with 2-butene, and compared to that of a Beta zeolite. In absence of deactivation (TOS=I min), zeolite ITQ-7 gives a higher proportion of C5-C7/C5+, obtained by cracking of C8 and specially of the bulky C9+. However, the main differences are observed in the distribution of the trimethylpentane (TMP) isomers. Although zeolite ITQ-7 is more selective to TMP in the C8 fraction than Beta, the most abundant isomers are 2,3,3- and 2,3,4-TMP instead of the primary 2,2,3-TMP or the thermodynamically favored 2,2,4-TMP. This is a clear shape selectivity effect, due to the smaller pore size of ITQ-7 as compared to Beta, and the fact that 2,3,3- and 2,3,4-TMP are the isomers with less restricted transition states and smaller diffusion problems.
276 2 4 - P - 2 1 - Butene isomerisation over ferrierite and SUZ-4 zeolite V.L. Zholobenko and C.L.T. Stevens
Keele University, Staffordshire, UK (fax.'44 1782 584352," e-mail. [email protected]) Medium pore zeolites have been evaluated as catalysts for n-butene isomerisation using a conventional continuous flow microreactor and a diffuse reflectance IR cell-reactor. The role of acid sites in ferrierite and SUZ-4 zeolite in this reaction and the mechanism of their deactivation have been investigated employing high temperature in-situ diffuse reflectance FTIR and on-line analysis of the products. The catalytic data show that both medium pore ferrierite and SUZ-4 zeolites are effective isomerisation catalysts providing high yield and selectivity towards isobutene. Further work, however, is required to optimise catalytic performance and hydrothermal stability of SUZ-4 zeolite. Enhanced selectivity and yield of isobutene obtained on the medium pore zeolites originate from the restricted transition state shape selectivity effects and a lowered concentration of the 'working' active sites, which favour the monomolecular reaction mechanism.
24-P-22 - Volatile products of the conversion of cyclohexene over A I - M C M - 4 1 M. Rozwadowski a, M. Lezanska a, J. Wloch a, K. Erdmann a, G. Zadrozna b and J. Kornatowski b
aFaculty of Chemistry, N. Copernicus Univ., Torun, Poland, mrozwad@chem uni. torun.pl bLehrstuhl H fiir Technische Chemic, Technische Universitcit Mfinchen, Garching, Germany The analysis of volatile products of the conversion of cyclohexene over A1-MCM-41 with various AI contents has revealed that the reaction runs mainly according to two mechanisms known as cyclohexene skeletal isomerization (CSI) and cyclohexene hydrogen transfer (HT). The results show which of the two schemes predominates, depending on the reaction temperature and the AI content of the catalyst. The processes of CSI and HT are accompanied by cracking and alkylation, which are proved by the presence of products with 1 to 9 carbon atoms even though the C6 compounds strongly prevail in all cases. Composition of the volatile products of the conversion depends on both concentration and strength of Br~nsted and Lewis acid centres. 2 4 - P - 2 3 - C u - Y zeolite catalysts for methanol and ethanol steam reforming M. Laniecki
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznah, Poland. Email: [email protected] Cu-Y zeolites were used as catalysts for the methanol and ethanol steam reforming for hydrogen generation. The effect of copper loading and the way of catalyst preparation on the structure and catalytic performance were examined. XRD, thermogravimetry, TPR, FTIR with adsorbed pyridine and hydrogen chemisorption were used to characterize Cu containing zeolites. The best catalytic performance was found for impregnated samples and CH3OH reforming. Catalysts acidity leads many undesirable reactions.
277
24-P-24 - Hexenes obtaining on the n i c k e l - ion exchanged zeolites M.K. Munshieva
Institute of Inorganic and Physical Chemistry, Azerbao'an Academy of Sciences, 370143, Baku, Azerbao'an Republic, 29 H.Javid Avenue, E-mail." [email protected] The dimerization of propylene in liquid phase over nickel-ion exchanged zeolites with various structures modified by treatment with A1Et2CI is studied. The mechanism of propylene dimerization on these catalysts is similar to the mechanism of olefin dimerization on ZieglerNatta catalytic systems. The different catalytic behaviours of the studied zeolites are connected with their crystalline structure. The X-ray investigation of the crystalline structure of zeolites after the repeated treatment with A1Et2C1 demonstrates its preservation.
24-P-25 - Catalytic sites of mesoporous silica in degradation of polyethylene A. Satsuma a, T. Ebigase a, Y. Inaki a, H. Yoshida a, S. Kobayashib, M.A. Uddin b, Y. Sakata b, and T. Hattori a
aDepartment of A~plied Chemistry, Nagoya University, satsuma@apchem, nagoya-u, ac.jp, Nagoya, Japan. Department of Applied Chemistry, Okayama University, Okayama, Japan Catalytic sites of mesoporous silica catalysts in degradation of polyethylene were investigated using characterizations by adsorption of NH3 and isohexane cracking. Siliceous materials gave a high liquid yield close to that of non-catalytic run, and degradation rate was enhanced by incorporation of aluminum. Mesoporous silica containing impurity level of aluminum exhibited as high activity as H-MFI and SIO2-A1203 with similar A1 content. The initial rate of degradation depended on the aluminum content and structure of mesoporous silica catalysts. FSM-16 exhibited exceptionally higher activity, which may be due to the presence of radical type catalytic sites on FSM-16.
24-P-26 - The nature of medium acidity in [CuO/ZnO/ZrO2]SAPO-34 hybrid catalyst for CO2 hydrogenation: study of the interactions between metal oxides and acid sites in zeolite S.-K. Ihm, S.-W. Baek, Y.-K. Park and K.-C. Park Dept. of Chem. Eng., KAI ST, Taejon, [email protected].~ ~, South Korea. Direct synthesis of hydrocarbons through carbon dioxide hydrogenation was investigated over hybrid catalysts composed of methanol synthesis catalysts (CuO/ZnO/ZrO2) and zeolites (HZSM-5, SAPO-34). New peak around 350~ due to the medium acidity appeared during the NH3-TPD of hybrid catalyst, and the areas of these new peaks were well correlated with the hydrocarbon yields in CO2 hydrogenation. The appearance of the new NH3-TPD peak was ascribed to the interaction between CuO/ZnO/ZrO2 and SAPO-34, which leads to the mutual changes in acidity of zeolite and reducibility of metal oxides.
278
24-P-27 - Reaction pathways for the aromatization of c y c l o h e x a n e and cyclohexene on Z n / H - Z S M - 5 zeolites A. Urd~ a, G. Tel'biz b and I. S~ndulescu a
a University of Bucharest, Faculty of Chemistry, Department of Chemical Technology and Catalysis, P.O. Box 12-241, Bucharest, Romania; [email protected] b Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Nauki Prospect 31, 252038, Kyev, Ukraine Aromatizations of cyclohexane and cyclohexene were studied on Zn/ZSM-5 catalysts with different zinc concentrations, at different residence times, with or without added gas (nitrogen or hydrogen). The results suggest that the first steps, at low Zn concentration, are the cracking of the feed molecule into unsaturated fragments and oligomerization. These are followed by a hydrogen transfer reaction, leading to aromatic compounds. Only at high zinc concentrations the direct dehydrogenation of the feed seems to play an important role.
24-P-28 - Coke species and coking m e c h a n i s m of S A P O - 3 4 in M T O process Y. Qi, G. Wang, Z. Liu, L. Xu, X. Gao and W. Cui
Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023, China, [email protected] The coking behavior of SAPO-34 in MTO process was investigated. The primary coking dynamics, the characteristics of coke species and the effects of coke deposition on catalyst performance were studied. It was found that the coke species differed with reaction temperature. The coke consists of both aromatics and oligomers at lower reaction temperature, while mainly of aromatics at higher reaction temperature. It is suggested that the coking mechanism at different reaction temperatures goes through different routes, i.e. through oligomerization at lower temperature while through aromatization at higher temperature.
24-P-29 - Pt-2,2'bipyridine complex encapsulated in Y zeolite - catalysts for ethylene selective dimerization R. Zavoianu and E. Angelescu
University of Bucharest, Dept. of Chemical Technology and Catalysis, bd. Regina Elisabeta no. 4-12, Bucharest-70346, Romania, fax. 04013159249, email: e_angelescu@chim, upb.rp This paper presents results concerning the synthesis of Pt(2,2'-bipyridine)C12 (K) encapsulated in Y zeolite and its activity in C2H4 selective dimerization to linear butenes. Diffuse reflectance UV-VIS spectroscopy and FTIR are used to investigate the state of the complex encapsulation. The influence of the reaction parameters on C2H4 selective dimerization to linear butenes is studied, we concluded that Pt(2,2'-bipyridine)C12 encapsulated in Y zeolite is a selective catalyst for ethylene dimerization to linear butenes at low temperatures (80 - 150~ and a reactant flow rate corresponding toWHSV 2h z .
279
24-P-30 - A r o m a t i c s formation from C 4 - C 4 = technical fraction over zincand z i n c / c o p p e r - c o n t a i n i n g Z S M - 5 zeolites N. Bilba (a), G. Iofcea (b), I. Asaftei (a), D.M. Padurariu (b) and C.C. Pavel (a) a "AI.I. Cuza" University of Iasi, Faculty of Chemistry, [email protected], Romania b S.C. "CAROM" S.A. Onesti, 5450 Onesti, Romania The catalytic and product distribution over HZSM-5, Zn-HZSM-5 and Zn-CuHZSM-5 during C4 - C4= (from catalytic cracking) conversion, have been studied. Product distributions at 123 K indicated that Zn-ZSM-5 and ZnCuZSM-5 exhibited higher aromatization activities compared with higher oligomerization activity of HZSM-5. Meanwhile, the time on stream increases from 24 h on HZSM-5 to 60 h on bifunctional catalysts and the resulting gases contain hydrogen only when metallic catalysts are used. Copper presence in ZnCu-HZSM-5 allows to work at 793 K without loosing Zn and obtaining a raw material composed only of nand/-butane.
24-P-31 - A r o m a t i z a t i o n of mixed-C4 h y d r o c a r b o n s over H Z S M - 5 catalysts modified by Zn and Ni cations L. Wei (a), J.Z. Gui (a), H.S. Ding (a), X.T. Zhang (a), H.Y. Li (a), L. Song (a,b), Z.L. Sun (a,*) and L.V.C. Rees (b) a Dept. of Appl. Chem., Fushun Petroleum Institute, Fushun, Liaoning, P. R. China, [email protected]; b Dept. of Chem., The University of Edinburgh, Edinburgh The aromatization of mixed-C4 hydrocarbons, prevalent by-products derived from petroleum refining processes, over HZSM-5 catalysts modified by both Zn and Ni cations via different impregnating methods has been systematically studied in two different sizes of reactors at various temperatures and space velocities of the feeds. The reaction mechanisms were discussed according to the liquid and gas product distributions. The acidity of the catalysts were also characterized using the frequency response (FR).
280
25 - Conversion of Aromatics (Tuesday) 25-P-06 - Isopropylation of naphthalene over large pore zeolites R.K. Ahedi, S. Tawada, Y. Kubota and Y. Sugi*
Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501-1193 (JAPAN). Email: [email protected]; Fax. 81-58-293-2597 [A1]-SSZ-31 was active in isopropylation of naphthalene, however, the selectivity was lower as compared to mordenite. Large pore zeolites viz. ZSM-12, CIT-5, SSZ-31, CIT-5 and HY were compared. CIT-5 and HY were very active, but, less selective. ZSM-12 and SSZ-31 showed better selectivity for 2,6-DIPN than CIT-5 and HY. Mordenite was the best catalyst.
25-P-07 - Shape-selective tert-butylation of biphenyl over H M , H Y and HI3 zeolites in the liquid phase D. Mravec(a), J. Homiakovd(a), M. Krdlik(a), M. Hronec(a), J. Joffre(b) and P. Moreau (b)
a, Slovak University of Technology, Bratislava, [email protected], Slovak Republic b, Ecole Nationale Sup6rieure de Chimie, Montpellier, France The alkylation of biphenyl with tert-butanol has been carried out over different zeolites under liquid phase conditions. HM (17.5) and HY (15) zeolites have been found to be the most active, with a maximum biphenyl conversion near 60 %. Dealuminated mordenite HM (17.5) leads to very high selectivities to 4-(tert-butyl)biphenyl (99%) and 4,4'-di(tert-butyl)biphenyl (96%). Selectivity to linear 4-TBB and 4,4'-DTBB depends on diffusional possibilities of relatively voluminous mono tert-butyl- and di (tert-butyl)biphenyl isomers from the zeolite pores. The most suitable temperature has been found to be 160 ~ An increase of the temperature leads to a significant decrease of selectivities to the desired products, as a result of secondary reactions.
2 5 - P - 0 8 - 1-Acetyl-2-methoxynaphthalene isomerization over zeolites. Effect of pore structure. V. Moreau, E. Fromentin, P. Magnoux and M. Guisnet
LCCO, UMR6503, University of Poitiers, patrick'rnagn~176
France.
Isomerization of 1-acetyl-2-methoxynaphthalene was investigated over HFAU, HBEA and HMFI zeolites (batch reactor, T=120~ Due to its pore size, HMFI was inactive for isomerization while HFAU is about 3 times more active than HBEA. This can be attributed to the easier desorption of the isomers from the HFAU pores. However, the selectivity of 2acetyl-6-methoxynaphthalene (the desired isomer) is favoured over HBEA. Analysis of the compounds retained in the zeolite pores show that the reaction occurs inside the micropores of the zeolites. Indeed, the desired isomer was found to be retained in the pores of HMFI showing that even for this zeolite, isomerization occurs in its micropores and that the desorption of the reaction products appears to be the limiting step.
281
25-P-09 - Alkylation of phenol with propylene over solid acid catalysts B. Wang*, C.W. Lee, T.-X. Cai* and S.-E. Park ~
Catalysis Center for Molecular Engineering, KRICT, P. O. Box 107, Yusung, Taejon 305-600, KOREA *School of Chemical Engineering, Dalian University of Technology,, P. R. China The alkylation of phenol with propylene over several solid acid catalysts such as HZSM-5 with different silica to alumina ratios, H-Beta, H-USY and 7-A1203 has been studied. It has been found that zeolite structure has great influence on product distribution. Apart from shape selectivity taking effect in phenol alkylation with propylene over HZSM-5 zeolites, acidic properties (i.e. acid strength and acid density) also influence product distribution. It has been found that H-ZSM-5 exchanged with different alkali metal ions, such as Na + and Cs + could apparently enhance the selectivity for para-iso-propylphenol due to the change of acidic properties. The acidic properties of the zeolites were characterized by NH3-TPD.
2 5 - P - 1 0 - Transalkylation of trimethylbenzene with toluene over large pore zeolites J. (~ejka (a), A. KrejU (a) and J. Hanika (b)
a J. Heyrovst9) Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic, cejka@l'h-inst.cas.cz b Department of Organic Technology, Institute of Chemical Technology, Technick6 5, CZ-166 28 Prague 6, Czech Republic The role of the channel geometry and architecture of large pore zeolites FAU, BEA and MOR on the activity, selectivity and time-on-stream stability in trimethylbenzene transalkylation with toluene to xylenes was investigated. It was found that the reaction mechanism is strongly controlled by the transport of reactant trimethylbenzenes and tetramethylbenzenes formed during the reaction. The highest yield to xylenes and long-term stability of conversion was achieved with zeolite BEA.
25-P-11 - Physicochemical characterization AI-HMS for N-methylation of aniline
and
catalytic
activity
of
J.M. Campelo, A. Garcia, D. Luna, J.M. Marinas, A.A. Romero and J.J. Toledano.
Departamento de Quimica Org(mica, Facultad de Ciencias, Universidad de C6rdoba, Campus Universitario de Rabanales, Edificio C3, [email protected], Spain AI-HMS mesoporous molecular sieves with Si/AI ratio in the range 10-40 were synthesized by using dodecylamine as template. They were characterized by XRD, N2 adsorption, MAS NMR, and DRIFT, and their acid properties were determined by pyridine (PY) adsorption. Aniline methylation was a pseudo-first-order process with respect to aniline concentration. Alkylation is a sequential reaction process, in which methylation of aniline produces Nmethylaniline (NMA), then N,N-dimethylaniline (NNDMA) and subsequently N,Ndimethyltoluidines (NNDMT, p- > o-). N-methylation products (NMA+NNDMA) were predominant with a selectivity over 97 mol% at 573 K.
282
25-P-12 - Catalytic activity of secondary aluminated mesoporous molecular sieve AIMCM-41 in the Friedel-Crafts reaction of bulky aromatic compounds H. Hamdan (a), A.B. Kim (b) and M.N. Mohd Muhid (b)
albnu Sina Institute for Fundamental Science, [email protected] bFaculty of Science, Universiti Teknologi Malaysia, UTM 81310, Johor, Malaysia Secondary aluminated MCM-41 (A1MCM-4 l(sec)) with Si/A1 ratio of 1.75 was synthesized. Characterization indicates that secondary alumination incorporates aluminium into the framework without affecting the long range order of the mesopores and structural stability of the framework. Friedel-Crafts alkylation of 2,4-di-t-butylphenol with cinnamyl alcohol catalyzed by the A1MCM-41 (sec) catalyst gave a high conversion. 29Si MAS NMR shows a different distribution of aluminium in the framework of MCM-41 by secondary synthesis as compared to direct synthesis. A1MCM-41 (sec) possesses Lewis and Br6nsted acidity and is a more efficient catalyst for reaction of large compounds.
25-P-13 - Naphthalene alkylation with methanol employing solid catalysts J. Aguilar-P, A. Corma a, J.A. de los Reyes b, L. Norefia, G. Mufioz, J.M. Sanchez, A. Torales and I. Hemdndez.
Area de Qu/mica Aplicada, UAM-A. Av. San pablo 180, CP 02200, Mdxico, D.F. a Instituto de Tecnologia Quimica, UP V-CSIC, Av. de los Naranjos s/n 46022, Val. Spain. b UAM-L Av. Michoacan y la Purisima, CP 09340, Mdxico, D.F. The relation between the structure of the catalyst and the reaction activity and selectivity was studied with MCM-22, MCM-41, HY, Beta and BZR5 catalysts. High selectivity in 13methylnaphthalene (2-MN) was obtained using MCM-41 catalyst. For the MCM-22 catalyst, the presence of 10 member ring (MR) channels and windows present severe constraint for the diffusion of naphthalene into the channels, therefore, the reaction possibly takes place at the external surface of this material. The order of activity is as follows: MCM-22 > Beta > HY > MCM-41 >BZR5.
25-P-14- Aikylation of biphenyl and naphthalene with propene. Is zeolite beta a shape-selective catalyst? D.M. Roberge and W.F. H61derich
Department of Chemical Technology and Heterogeneous Catalysis, R WTH-Aachen, Worringerweg 1, D-52074 Aachen, Germany, [email protected]. An acid treated zeolite beta with a 6 M HNO3 acid solution is a shape-selective catalyst for the alkylation of biphenyl with propene. This is however not the case for the alkylation of naphthalene. The reaction is highly mass transfer limited and the selectivity mechanism is attributed to a product selectivity. The major effect of the acid treatment is to deactivate the external surface area so that the intrinsic micropore properties can come out. Contrary to zeolite mordenite, the acid treatment does not reduce deactivation and the formation of highly aromatic coke remains important at high temperatures.
283
25-P-15- Aikylation of benzene by propane with participation of space divided centres S.I. Abasov, R.R. Zarbaliyev, G.G. Abbasova, D.B. Tagiyev and M.I. Rustamov
Institute of Petrochemical Processes, Academy of Sciences of Azerbaijan 30 N.Rafiyev st., Baku-370025, Azerbaijan Republic Fax." (9412) (90-35-20); E-mail. [email protected],[email protected] The benzene alkylation by propane has been investigated using a zeolite-containing catalyst. The isopropylbenzene formation is shown to begin at 180-350~ over HY and Pt, Re/A1203 admixed catalysts. The temperature increase leads to C3H6(250~ and other alkylbenzenes (300~ formation. The by-products may be reduced by the selective poisoning of Br6nsted acidic centres by ammonium. From the considerations on the reaction, the probable mechanism of benzene dehydroalkylation by propane has been proposed.
25-P-16 - Alkylation of isopropylnaphthalene over heteropoly acid catalysts supported on mesoporous materials M.-W. Kim a, W.-G. Kim a, J.-H. Kim a, Y. Sugi b and G. Seo a
~Department of Chemical Technology & The Research Institute for Catalysis, Chonam National University, Gwang/u 500- 75 7, Korea bDepartment of Chemical, Faculty of Engineering, Gifu University, Gifu 501-1193, Japan The isopropylation of 2-isopropylnaphthalene was studied over heteropoly acid catalyst supported on mesoporous material. The physico-chemical state of loaded heteropoly acid was investigated using XRD, nitrogen adsorption measurement and FT-IR techniques. Heteropoly acid was highly dispersed on the wall of mesoporous material, and retained its Bronsted acidity. The conversion and the selectivity for [3, 13 -diisopropylnaphthalene were very high over the mesoporous material with a large loading amount of heteropoly acid. The treatment of heteropoly acid was helpful for the improvement of the acidity of mesoporous material.
25-P-17 - Highly selective isopropylation of xylenes catalyzed by zeolite Beta C.R. Patra, S. Kartikeyan and R. Kumar
Catalysis Division, National Chemical Laboratory, Pune 411 008, INDIA raj [email protected] 1.res. i n) The isopropylation of xylenes to form corresponding dimethyl cumene(s) was carried out with isopropanol over large pore high silica zeolite H-beta as catalyst under continuous vapor phase fixed bed down flow glass reactor system at atmospheric pressure and moderate temperatures (413K to 453K). Zeolite H-Beta exhibited quite high activity, selectivity and stability. The effect of reaction temperature, space velocity, substrate to alkylating agent molar ratio and time-on-stream on conversion and selectivity was studied. As high as 90-99 % selectivity for dimethylcumene(s) was obtained in relatively lower reaction temperature range of 413-433 K at quite high xylene conversion (80-90% of theoretical value).
284
08- Syntheses with Non-Ionic surfactants (Wednesday) - The double-step synthesis of MSU-X silica: decoupling the assembly mechanism 08-P-05
E. Prouzet*, C. Boissi&e, N. Hovnanian and A. Larbot. Institut Europden des Membranes, L.M.P.M. (CNRS UMR 5635) Universitd Montpellier II, CC 047, F-34095, Montpellier, cedex 5, FRANCE. e-mail : [email protected] In a new double-step synthesis of MSU-X type silicas, which was reported previously, a first step allows the preparation of a colorless stable and homogeneous aqueous solution where both nonionic surfactants and silica oligomers are mixed. Dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and 29Si NMR analyzes revealed that this first step allows the assembly of surfactants and silica oligomers in specific micellar hybrid objects that are described.
0 8 - P - 0 6 - S t e a m - stable aluminosilicate MSU-S mesostructures assembled
from zeolite seeds
Yu Liu, W. Zhang and T.J. Pinnavaia Department of Chemistry, Michigan State University, [email protected] The hydrothermal stability and acidity of aluminosilicate mesostructures can be improved substantially through the surfactant - directed assembly of protozeolitic aluminosilicate nanoclusters that normally nucleate (seed) the formation of microporous zeolites. Our results indicate that zeolite type Y, Beta, and ZSM-5 seeds are particularly effective at forming steam stable aluminosilicate mesostructures, which we generally denoted as MSU-S.
0 8 - P - 0 7 - A Study on the mesoporous silica structures templated by triblock
copolymers C.-P. Kao(a), H.-P. Lin(b), M.-C. Chao(a), H.-S. Sheu(c) and C.-Y. Mou(a)*
a National Taiwan University, Taipei, [email protected], Taiwan b Institute of Atomic and Molecular Sciences Academia Sinica, Taipei, Taiwan c Synchrotron Radiation Research Center, Hsinchu, Taiwan The well-ordered mesostructures SBA-15 or SBA-16 could fast grow from the chemical composites of triblock copolymers (EOnPOmEOn)-TEOS-HC1-H20. At the desired TEOS/EOz0PO70EO20 ratio, an organic surfactant-silica macrosphere of about 1 cm was successfully obtained, and the organic-inorganic mesostructural macrospheres have the particularly elastic property. Post-hydrothermal treatments at high temperature promoted the increase of the unit cell and pores.
285
08-P-08 - Study of methyl modified M S U - X silicas Y. Gonga, Z. Lia, S. Wanga, D. WUa, Y.-H. Suna, F. Dengb, Q. Luob and Y. Yueb a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences(CAS), Taiyuan China bState Key Laboratory of Magnetic Resonance and Atomic Molecular Physics, Wuhan Institute of Physics and Mathematics, CAS, China Methyl-modified MSU-1 mesostructures were prepared by one-pot strategy. The microstructure and the interfacial characteristic were measured with N2 sorption, IR, 29SiNMR, SEM, TEM, TGA and SAXS. The results showed that methyl groups have been incorporated into MSU-X silica framework and the surface and texture properties of the resultant materials varied with the amount of incorporated methyl groups.
08-P-09 - Study of mesoporous materials with ultra high surface area prepared from alternate surfactants and silicate sources J.F. P4rez-Ar~valo a'b, J.M. Dominguez c, E. Terr6s c, A. Rojas-Hem~indez b and M. Miki d a UNAM,, FES-Cuautitl6n, b UAM-I, c1MP, aCIMAE [email protected] A comparison study on the synthesis of mesoporous materials from Triton X-100/Nametasilicate and CTAB/TEOS was performed and their textural and structural parameters were characterized by XRD, N2 adorption and TEM. The CTAB/TEOS solids presented high surface mesopore areas, exceeding 1100 m2/g, while the Triton X-100/Na-metasilicate presented areas from 1200 up to 1467 m2/g. The analysis of the textural data indicated that upon calcination pore sintering occurs in the Triton/Na-metasilicate solids, while it does not occurs in the CTAB/TEOS system. This is probably due to the different packing effective factor of the surfactant molecules.
08-P-10 - Synthesis and catalytic properties of SO3H-mesoporous materials from gels containing non-ionic surfactants I. Diaz, F. Mohino, E. Sastre and J. P6rez-Pariente Instituto de Cat6lisis y Petroleoquimica, C.S.1.C., esastre@icp, csic. es, Madrid, Spain A variety of mesoporous silicates containing mercaptopropyl groups have been prepared by direct synthesis from gels containing non-ionic surfactants. By adjusting properly several synthesis parameters, thiol-containing SBA-15 have been obtained from gels containing Pluronic 123, whereas a stable material probably related with SBA-12 has been synthesized from Brij 76. These materials possess large surface areas and pore sizes of 3.2 and 1.8 nm, respectively and have been structural characterized by transmission electron microscopy. The oxidation of the thiol groups with hydrogen peroxide leads to sulfonic acid groups which have been shown to catalyze the esterification of glycerol with oleic acid. Factors affecting the catalytic performance of these materials are discussed.
286
08-P-I1 - Secondary hydrolysis process to synthesize highly ordered mesoporous silica from nonionic surfactant with long hydrophilic chain J. Fan, C. Yu and D. Zhao*
Department of Chemistry, Fudan University, Shanghai 200433, P. R. China dyzhao@)Cudan,edu. cn In this paper, we have demonstrated a simple secondary hydrolysis process to synthesize a highly ordered hexagonal mesoporous silica structure by using nonionic oligomeric surfactant with long hydrophilic chain. This process involves an adsorption step of extra silica source and secondary hydrolysis process and can result in large improvement on the ordering and hydrothermal stability for the mesoporous silica materials.
08-P-12 - Mesostructure design using mixture of nonionic amphiphilic block copolymers 9
a
J.M. K l m , S.-E. Park a and G.D. Stucky b
a Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology (KRICT), P.O. Box 107, Yusong, Taejon 305-600, Korea; separk@pado, krict, re. kr b Department of Chemistry, University of California, Santa Barbara, CA 93106, USA Formation of mesoporous silica materials has been studied using mixtures of amphiphilic diblock copolymers (CnH2,+I(OCH2CH2)xOH, C,EOx, n = 12 - 18 and x = 2 - 100) as the structure directing agents and sodium silicate as the silica source. Results obtained from X-ray diffraction patterns and transmission electron microscopy indicate that silica/polymer mesostructures are transformed from lamella to 2-d hexagonal (P6mm), 3-d hexagonal (P6y'mmc), cubic Pm3m and cubic Im3m, as the size (x) of hydrophilic head group increases. Optimum ratios between the hydrophilic EO groups and hydrophobic tail groups are investigated in order to obtain highly ordered mesoporous silica materials.
08-P-13 - Stability of mesoporous material SBA-15 and its benefit in catalytic performance C. Nie, L. Huang, D. Zhao and Q. Li*
Dep. Chem., Fudan University, Shanghai 200433, P. R. China qzli@)Cudan.edu.cn The stability of mesoporous material SBA-15 and A1-SBA-15 was investigated under steaming treatment (100 % H20) at 800 ~ for different time. A1-SBA-15 catalyst has been prepared via post-synthesis procedure. The results show that the mesostructure of SBA-15 and A1-SBA-15 can be retained at 800 ~ steaming for 8 h, while MCM-41 totally loses its mesostructure under the same condition just for 2 h. Moreover, A1-SBA-15 still has cracking activity of n-hexadecane and Pt/A1-SBA-15 has hydroisomerization activity of n-dodecane to some extent even after steaming treatment at 800 ~ for 8 h. Meanwhile, A1-MCM-41and Pt/A1-MCM-41 catalysts totally lose their activity under the same treatment condition just for 2h.
287
08-P-14 - Comparative study of the wall properties in highlyordered silicate and aluminosilicate mesostructured materials of the MCM-41 and SBA-15 types L.A. Solovyov (a), V.B. Fenelonov (b), A.Y. Derevyankin (b), A.N. Shmakov (b), E. Haddad (c), A. Gedeon (c), S.D. Kirik (a) and V.N. Romannikov (b). a Institute of Chemistry and Chemical Engineering, [email protected], infotel.ru. b Boreskov Institute of Catalysis: [email protected] c Universit6 P. et M. Curie [email protected]. X-ray diffraction structural modeling based on a continuous electron density representation and textural analyses by the combined XRD-adsorption method were applied for to quantify distinctions in the wall structure of the MCM-41 and SBA-15 types of mesostructured materials.
288
09-Crystal Structure Determination (Wednesday) 09-P-06 - Crystal structure of a cadmium sorption complex of dehydrated fully Cd(II)-exchanged zeolite X E.Y. Choi a, S.H. Lee a, Y.W. Han b, Y. Kim a and K. Seff c
aDepartment of Chemistry, Pusan National University, Pusan, Korea, [email protected] bDepartment of Science Education, Pusan National University of Education, Pusan, Korea CDepartment of Chemistry, Universityof Hawaii, 2545 The Mall, Honolulu, Hawaii 96822, U. S. A. A single crystal of fully dehydrated Cd2+-exchanged zeolite X, Cd46SiI00A1920384, was exposed at o
320 C to 0.005 Torr of Cd vapor for 9 d. The resultant crystal, Cd68SiI00A1920384 (a = 24.953(6) A), was studied by single-crystal XRD techniques in the cubic space group Fd-3 m at 21(1) ~ In this structure, Cd species are found at seven sites. Twenty-eight Cd 2+ are found at sites I', II', and II with occupancies of eight, six, and fourteen. Thirty-six Cd + are found at sites I, I', and II with occupancies of six, eighteen, and twelve. The eight Cd 2+ at I' associate with four Cd ~ atoms (II') to form four bent Cd2+-Cd~ 2+ clusters per unit cell in the sodalite cavities.
09-P-07 - The structure of a copper molybdate and its relation to other natural and synthetic porous materials based on transition metal polyhedra L.A. Palacio (a), A. Echavarria (a), A. Simon (b) and C. Saldarriaga (a)*
(a)Department of Chemical Engineering, University of Antioquia A.A. 1226, Medellin, Colombia ([email protected]) (b)Laboratoire de Materiaux Mineraux, UPRES-A-7016, C.N.R.S., 3 rue Alfred Werner 68093 Mulhouse Cedex, France A new non-stoichiometric copper molybdate of ideal composition (NH4OH)3/2(CuMoO4)2 was synthesized hydro thermally and its crystal structure was solved from powder data. The material shows the hexagonal parameters a=6.0775(3) and c=21.601(1) A in the space group R-3m. The green powder exhibits the same building units observed in the mineral Volborthite and the layered structure of other materials based on transition metal polyhedra.
0 9 - P - 0 8 - A 3-D Open-framework nickel aluminophosphate [NiAIP2Os][C2N2H9]" assembly of I-D AIP2Os a" chains through [NiOsN] octahedra B. Wei a, J. Yu a, G. Zhu a, F. Gao a, Y. Li a, R. Wang a, B. Gao a, Xian. Xua,S. Qiu a* and O. Terasaki b
aKey Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry, Jilin University, Changchun 130023, P. R. China,e-mail." [email protected]; bCREST; Department of Physics, Tohoku University, Sendai 980-8578, Japan A 3-D Open-framework [NiA1P208][C2NzH9] (NiAPO-1) was synthesized successfully in a solvothermal system. Its structure was solved by CCD single crystal X-ray diffractometer, with Monoclinic, space group P21/c (No. 14), a=8.542(2) A, b=15.564(3) A, c=7.627(1) A, and [3=110.60(1) ~ V=949.1(3)A 3, Z=4, assemblied by 1-D A1P2083- and 1-D [Ni-O-Ni] chains. It was characterized by powder X-ray diffraction, thermogravimetric/differential thermal analysis, ICP, element analysis, 27A1, 31p MAS NMR and magnetic measurement.
289
09-P-09- Structural modifications induced by high pressure in scolecite and heulandite: in-situ synchrotron X-ray powder diffraction study G. Vezzalini a, S. Quartieri b, A. Sani c and D. Levy d
~Dipartimento di Scienze della Terra, Universitg~ di Modena, Italy, giovanna@unimo, it bDipartimento di Scienze della Terra, Universit~t di Messina, Italy ~INFMand European Synchrotron Radiation Facility, Grenoble Cedex, France dDipartimento di Scienze Mineralogiche e Petrologiche, Universitdt di Torino, Italy We present an in-situ synchrotron X-ray powder diffraction study on the compressibility and the pressure-induced structural modifications in scolecite and heulandite. The cell parameter refinements were carried out up to 7.5 GPa and 6 GPa for scolecite and heulandite, respectively. The HP-induced deformations of both zeolites can be interpreted on the basis of the mechanisms observed during the dehydration processes of the two minerals. Heulandite amorphization process is reversible and occurs at a lower pressure.
09-P-10- Preparation, characterization, and crystal structures of fully indium-exchanged zeolite X N.H. Heo, a S.W. Jung, a S.W. Park, a J.S. Noh, a W.T. Lim, b M. Park a and K. Seff c
aDqpartment of Industrial _Chemistry, Kyungpook National University, Taegu 702-701, t~htieo~kvungpook, ac. kr, Korea ~ Accelerator Laboratory Pohang Institute of Industrial Science & Technology, P. O. Box 12S. Pohang 790-600, wtlimJ'~g)ostec~h.ac.kr, K6rea CDepartment of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822-2275, [email protected], U. S. A. o
In-X has been prepared by solvent-free redox ion-exchange of T1-X with In metal at 350 C. EPXMA showed the product to be an indium aluminosilicate (ca. 47 wt% In) free of T1. Single crystal X-ray diffraction and XPS experiments showed that In-X contained indiums in various oxidation states. In+ and In2+ ions are found at a variety of 3-fold axis and supercage sites, and In5n+ clusters are seen at the centers of some sodalite cavities. Exposure to the atmosphere, washing with H20, and redehydration caused only a small change in + 7+ composition, from (In+)v8(In57+)2-X to (In)74 5(In5 )2 5-X, with a change of space group from Fd3 to Fd3m.
09-P-11 - Structural investigation by powder X-ray diffraction and solid state nuclear magnetic resonance of AIPO4-SOD M. Roux a, C. Marichal a, J.L. Paillaud a, L. Vidal a, C. Femandez b, C. Baerlocher c and J.M. Chezeau a
a Laboratoire de Matdriaux Min6raux, ENSCMu,, [email protected], France. b Laboratoire de Catalyse et Spectrochimie, ISMRA, 14050 Caen, France. c Laboratoriumfiir Kristallographie, ETH, CH-8092 Z~rich, Switzerland The crystalline structure of A1PO4-SOD, an aluminophosphate, was investigated by high resolution powder X-ray diffraction and various solid state nuclear magnetic resonance (NMR) techniques. In particular, 31p homonuclear correlation and 27A1/31P 3QHETCOR NMR experiments allowed the complete assignment of 3~p and 27A1 resonances to the corresponding crystallographic sites. All results from the different NMR techniques are compared with the refined structure resulting from a Rietveld analysis on powder synchrotron data.
290
09-P-12 - Layered germanates with 9-membered rings X. Zou, T. Conradsson and M.S. Dadachov
Structural Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden Two germanates, (NH4)4[(GeO2)3(GeOI.sF3)2]'0.67H20 and (C2N2HI0)2[(GeO2)3(BO2.5)2], were prepared by hydrothermal synthesis. The framework layers are formed by 3- and 9membered rings in both compounds and the structure topology within the layers is very similar. The 3-membered rings in both compounds are built by three GeO4 tetrahedra. These 3-rings are connected by pairs of GeO3F3 octahedra in (NH4)4[(GeO2)3(GeO1.sF3)2]'0.67H20 and by pairs of BOa tetrahedra in (C2N2Hlo)2[(GeO2)3(BO2.5)2] in such a way that 9-membered rings are formed. The framework layers are interrupted by ammonium cations and water molecules in the former compound and protonated ethylenediamine in the latter compound. The 2D frameworks of the germanate and the borogermanate are compared with other related structures.
0 9 - P - 1 3 - Dehydration dynamics of mordenite by in-situ time resolved
synchrotron powder diffraction study: a comparison with electrostatic site energy calculations. A. Martucci, M. Sacerdoti and G. Cruciani
Dipartimento di Scienze della Terra, Sezione di Mineralogia, Universith di Ferrara, Corso Ercole I d'Este, 32, 1-44100 Ferrara, Italy; e-mail: [email protected] The structural transformation of a natural mordenite by in-situ heating to 830~ was studied, using Rietveld structure analysis. At 830~ mordenite maintains the space group Cmcm and behaves as a non-collapsible framework, featuring only a slight cell volume contraction (-1.9%) related to the water release. The removal of water molecules was accompanied by a migration of the cation sites near the framework oxygens. The extra-framework cation positions in dehydrated mordenite were also simulated by electrostatic energy calculations.
09-P-14 - Study of water vapor adsorption in the organically-lined channels of AIMepO-[3 using X-ray powder diffraction K. Maeda (a,b), L.B. McCusker (a) and C. Baerlocher (a)
Laboratory of Crystallography, ETH-Zurich, Zurich, Switzerland bNational Institute of Advanced Industrial Science and Technology (National Institute of Materials and Chemical Research), Tsukuba, [email protected], Japan The structural changes in the framework of the aluminomethylphosphonate A1MepO-13 upon water vapor sorption and the location of the sorbed water molecules have been investigated using X-ray powder diffraction techniques. Only small differences between the framework structures of the degassed and the water-sorbed sample were found. However, the latter did contain additional water positions in the channels. The differences between the water sorption behavior of the two polymorphs of A1MepO (-cz and-13) are discussed.
291
20 - Zeolite Membranes and Films (Wednesday) 2 0 - p - 0 6 - Dehydrogenation of ethylbenzene to styrene using ZSM-5 type zeolite membranes as reactors X.-F. Zhang, Y.-S. Li, J.-Q. Wang, H.-O. Liu and C.-H. Liu
Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, 158 Zhongshan Road, Dalian 116012, [email protected], China. Factors on dehydrogenation of ethylbenzene to styrene in ZSM-5 type zeolite membrane reactors were studied. About 18% conversion of ethylbenzene increase in the Fe-ZSM-5 membrane reactor can be obtained over the fixed-bed reactor. This result is better than that obtained in the other membrane reactors. The bigger is the permeability and permselectivity of ZSM-5 membranes, the higher is the conversion of ethylbenzene. The order of membrane stability for ethylbenzene dehydrogenation is silicalite-1 > Fe-ZSM-5 > Fe/ZSM-5 > ZSM-5.
2 0 - P - 0 7 - Preparation of high-permeance ZSM-5 tubular membranes by varying-temperature synthesis Y.-S Li, Xio. Zhang, J.-G. Wang and S. Guo
Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, Dalian, 116012, China, [email protected] In this work, high-permeances ZSM-5 zeolite membranes were synthesized on porous a-alumina tubes by a varying-temperature in-situ hydrothermal treatment using n-butylamine(NBA) as a template. The membranes were characterized by XRD, SEM and single-gas permeation measurements. The highest H2 permeance is up to 2.3x 106mol/m2.s.Pa, the highest ideal selectivities are 201 for H2/n-C4Hl0, 13 for n-C4Hlo/i-C4Hlo, at 293 K. Few non-zeolite pores formed in the membrane when the sol was renewed during the varying-temperature process, so that the membrane had high ideal selectivity of n-C4Hlo/i-C4Hlo above 473 K. The separation properties of the membranes were largely determined by synthesis procedure.
20-P-08 - Synthesis of FAU type films on steel supports using a seeding method Z. Wang, J. Hedlund and J. Sterte
Division of Chemical Technology, Lulegt University of Technology, [email protected], Sweden FAU type films were synthesized on polished steel supports using a seeding method. The feasibility of the method was demonstrated for a wide variety of steel types. After 12 h of synthesis the film was continuous with a thickness of about 2 gm. A prolonged synthesis time in one single step resulted in significant attachment of sediments on the film surface for some preparations. Several identical 12 h synthesis steps were therefore used to increase the thickness of the films by approximately 2 ~tm with each additional synthesis step. Morphology and film thickness was independent of steel type. All films were continuous and crack free prior to calcination.
292
20-P-09 - Structured zeolite ZSM-5 coatings on ceramic packing materials O. Ohrman, U. Nordgren, J. Hedlund, D. Creaser and J. Sterte
Luledt University of Technology, Sweden. Email."[email protected] Homogeneous coatings of zeolite ZSM-5 were prepared by the seed film method on porous ceramic foams and on alumina spheres. The zeolite was predominately present in the form of a film on the support surface rather than as aggregated crystals on the surface. The results from gas adsorption and SEM analysis indicated that the entire surface of the foams was successfully covered with a 450 nm film. A 500 nm film was formed on the external surface and also in pores close to the external surface of the spheres. Zeolite was not formed on the internal surface of the alumina spheres. Aluminum leaching from the foams was observed but did not seem to have any detrimental effects on the substrates.
20-P-10 - Effects of synthesis parameters on intra-pore zeolite formation in zeolite A membranes M. Lassinantti, J. Hedlund and J. Sterte
Division of Chemical Technology, Lule~t University of Technology, [email protected], Sweden Na-A films were synthesized on porous substrates using a seeding technique. Effects of synthesis temperature, synthesis duration and gel composition on the morphology of the films were evaluated. Higher synthesis temperature resulted in relatively more growth of zeolite into the porous support compared to the film growth on top of the support. By using a multistep synthesis procedure at low temperature, thicker films with less growth into the support could be prepared.
20-P-II Pure-silica zeolite Iow-k dielectric thin films by spin-on process Zhengbao Wang, H. Wang, A. Mitra, L. Huang and Y. Yan*
Department of Chemical and Environmental Engineering, University of California, Riverside, CA 92521, USA; yushan,[email protected]. Spin-on silicalite thin films were prepared from silicalite nanocrystals. Spin-on silicalite films with high porosity have a dielectric constant (k) of 1.8-2.2. A secondary growth of nanocrystals was carried out on spin-on films under microwave treatment. It was found that a secondary growth of nanocrystals by microwave treatment could increase the mechanical strength and control the inter-particle pore size and porosity of spin-on silicalite films. Microwave-treated spin-on films have a k value of 2.2-2.4. The effect of moisture on k value was also studied. The silylation of silicalite films with chlorotrimethylsilane was conducted to eliminate the effect of moisture on the dielectric constant. It was revealed that stable k values were obtained after silylation.
293
20-P-12 - Preparation of silicalite-I and beta zeolite/ceramic composite membranes and removal of trace phenol and benzene from water through them Xiansen Li and S. Xiang* Department of Chemistry, Nankai University, Tianjin, [email protected], P. R. China The in-situ syntheses of silicalite-1 and beta zeolite membranes on the ceramic filter substrates were performed. The physico-chemical properties of the zeolite composite membranes were characterized by XRD, SEM and UV. The removal of phenol and benzene from water through the zeolite composite membranes was studied. It was found that silicalite1 and beta membranes possessed good separation ability for PhOH/H20 and C6H6/H20 and that beta membrane was better than that of silicalite-1 for PhOH/HzO. The average rejection rates of beta and silicalite-1 membranes for PhOH/H20 were 69.9% and 51.5% respectively. The separation capacity of silicalite-1 zeolite membrane for PhOH/H20 and C6H6/H20 increased after twice synthesis and steam treatment
20-P-13 - Factors affecting film thickness in the preparation of supported ZSM-5 zeolite E.I. Basaldella, A. Kikot, J.F. Bengoa and J.C. Tara Centro de Investigaci6n y Desarrollo en Procesos Cataliticos (CINDECA), Universidad Nacional de La Plata, CONICET, CIC, 47 N~ (1900) La Plata, Argentina. The growth of hydrogel based ZSM-5 zeolite films on cordierite monoliths was studied varying some specific synthesis parameters. More diluted gels decrease the simultaneous production of loose crystals without altering the characteristics of the film formed, while a temperature decrease leads to similarly thick films, though made up of smaller crystals. As films of about the size of a crystal were obtained by increasing acid addition, it would be possible to control film thickness by changing the acidity of the medium. Besides, stirring proved to be essential to obtain uniform coating.
20-P-14 - Growing zeolite films onto gold surfaces E.I. Basaldella a, A. Kikota, J.O. Zerbino b and J.C. Taraa aCentro de Investigaci6n y Desarrollo en Procesos Cataliticos (CINDECA), Universidad Nacional de La Plata, CONICET, CIC, 47 N~ (1900)La Plata-Argentina. blnstituto de Investigaciones Fisicoquimicas Te6ricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, CIC, C. C. 16, Suc. 4, (1900) La Plata- Argentina Silicalite layers were hydrothermally synthesized on gold surfaces by the in-situ crystallization method, using hydrazine and oxigenated water as additives. In this way, it is possible to alter the gold-zeolite electrostatic interaction by changing the electric charge of the metal surface. The effects on the layer growth process related with this change are discussed. Besides, it is proved that metal roughness improves the zeolite layer adherence.
294
20-P-15 - Diffusivities of zeolite coatings M. Tather, ~;.B. Tantekin-Ersolmaz and A. Erdem-$enatalar
Department of Chemical Engineering, Istanbul Technical University, Maslak, 80626 Istanbul, (aerdem@itu. edu. tr), Turkey A method was proposed for the determination of the diffusivities of zeolite coatings. The simulation of the operation of a thermogravimetric analyzer by modeling studies together with experimental TGA measurements allows the estimation of the diffusion coefficient whenever relatively thick zeolite coatings, for which mass transfer resistances exist, are available. The diffusion coefficient of the zeolite 4A-water pair obtained by using the method developed was quite close to the value measured by using the PFG NMR method. This deduction could be made by taking into account the results obtained for a consolidated 4A powder sample and a coating prepared by repeated syntheses. Relatively higher apparent diffusivities were obtained for the relatively thicker zeolite 4A coatings prepared by using the direct heating method, which leads to the formation of coatings with more open structures.
20-P-16 - Crystal growth mechanism of LTA and FAU and densification process of zeolite film by seed growth I. Kumakiri a* , Y. Sasaki,b W. Shimidzu,b T. Yamagushi a and S.-I. Nakao a
aDepartment of Chemical @stem Engineering, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan, bResearch and Development Laboratory, Japan Fine Ceramics Centre, 2-4-1, Mutsuno, Atsuta-ku, Nagoya, 456-8587, Japan Zeolite NaA and FAU crystals were grown under the same hydrothermal condition using the same composition of clear solution. The only difference was the type of seed crystal used. This result suggested that the crystal growth did not occur by the attachment of nano-crystals. Zeolite films/membranes were prepared by the growth of seeded crystals. Based on the SEM and TEM observations and single gas permeation measurements, densification model of film/membrane is presented.
20-P-I 7 - In-situ synthesis of ZSM-5 on aluminum surfaces F. Scheffier and W. Schwieger
Institute of Industrial Chemistry I, University of Erlangen-Nuremberg Egerlandstr. 3, D-91058 Erlangen, Germany In this study the hydrothermal formation of ZSM-5 zeolitic coatings o n the surface of different pretreated flat aluminum sheets has been investigated. The specific feature of the reported preparation method is the fact that the aluminum sheet acts as a support as well as an aluminum source as well to achieve a good connection between the support and zeolite layer. The reaction was carried out under various synthesis conditions. The obtained products were characterized by XRD, SEM and chemical analysis.
295
20-P-18 - Conceptual process design of an all zeolite membrane reactor for the hydroisomerization of CJC6 E.E. McLeary a*, R.D. Sanderson a, C. Luteijn ~, E.J.W. Buijsse b, L. Gora b, T. Maschmeyer b and J.C. Jansen a'b
~Institute of Polymer Science, Faculty of Natural Science, Stellenbosch University, South Africa," bLaboratory of Applied Organic Chemistry and Catalysis, Delft University of Technology, Delft, The Netherlands," CLaboratory of Process Systems Engineering, Delft University of Technology, Delft, The Netherlands Membrane reactors provide opportunities for overcoming thermodynamic limits on the maximum attainable conversion of reversible reactions. A simple membrane reactor model has been employed to investigate the performance of C5/C6 hydroisomerization process on zeolites and compare it to a state-of-the-art total isomerization (TIP) process. A RON of 88.0 was obtained, slightly higher and promising compared to the TIP process with RON of 86.
296
21 - Nanocomposite Fundamentals and Applications (Wednesday) 21-P-06- Fabrication of hollow fibers and spheres composed of zeolites by layer-by-layer adsorption method Y. Tang (a), Y.-J. Wang (a), X.-D. Wang (a), W.-L. Yang (b)and Z. Gao (a)
a Department of Chemistry, Fudan University, Shanghai 200433, China, yitang@)Cudan.edu.cn b Department of Macromolecular Science, Fudan University, Shanghai 200433, China Hollow fibers and spheres of zeolite (labeled as HFZ and HSZ, respectively) were successfully fabricated using carbon fibers and polystyrene (PS) spheres as templates respectively, through layer-by-layer technique, coupled with removal of the templates by calcination. The optimum performance conditions to obtain these kinds of materials were systematically studied. The wall thickness and composition of these novel materials can be readily tailored by varying the number of nanozeolite/PDDA (poly(diallyldimethyl ammonium chloride)) deposition cycles and zeolite type used, respectively. The properties of these novel materials were characterized by means of XRD, IR and SEM.
21-P-07- The zeolitisation of diatoms to create hierarchical pore structures S.M. Holmes(a), R.J. Plaisted(b), P. Crow(b), P. Foran(b), C.S. Cundy(b) and M.W. Anderson(b)
a Environmental Technology Centre, Chemical Engineering Dept. UMIST, Sackville Street, Manchester, M60 1QD, UK. e-mail." [email protected], fax: +44 161 2004399 b UMIST Centre for Microporous Materials, Sackville Street, Manchester, M60 1QD, UK. The synthesis of a hierarchical pore structure, combining the macroporous diatomaceous earth with microporous zeolites, is reported. Diatomaceous earth is an abundant and varied source of macroporous silica which has been 'zeolitisatised' to produce a bifunctional, hierarchical composite. A range of different zeolites have been synthesised to generate different pore architectures, hydrophobic/hydrophilic materials and ion-exchange/catalytic properties.
21-P-08 - Generating the narrowest single-walled carbon nanotubes in the channels of AIPO4-5 single crystals G.D. Li (a,b), Z.K. Tang (b), N. Wang (b), K.H. Wong (b) and J.-S. Chen* (a)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, [email protected], edu. cn, Changchun, P. R. China b Department of Physics, HKUST, Hong Kong, P. R. China The pyrolysis of tripropylamine trapped in the framework structure of A1PO4-5 (AFI) single crystal results in the formation of the narrowest single-walled carbon nanotubes. The diameter of the nanotubes, which are stable enough when located in the AFI channels, is 0.42+0.02 nm. As the nanotubes are strictly aligned in the one-dimensional channels, the AFI crystal containing the tubes shows distinct anisotropic property. The growing process of the nanotubes was monitored by polarized optical microscopy. It has been found that the optimal temperature range for the growth of the nanotubes in A1PO4-5 single crystals is 773-873 K.
297
2 1 - P - 0 9 - Zeolite- an effective nucleating agent of Na2HPO4"I2H20 J. Dong, X. Jing and Yu. Zhang
Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, Shanxi, P. R. China, [email protected] The use of zeolites, including LTA, Y, LTL, VPI-7, MFI and MOR, as nucleating agents of phase-change-material Na2HPO4"12H20 was first reported. The results showed that all the selected zeolites could inhibit the supercooling of Na2HPO4"12H20 to some extent. Among them MOR displayed the best effect. When the amount is 5%, it can lower the supercooling to 2.03---1.02~ and this system showed good stability and reversibility. At the same time, the morphology of samples after many times of re-crystallization was studied with SEM. The photograph of the SEM and microprobe analysis results showed that these different zeolites could form mixed isomorphous crystals with NazHPO4" 12H20. The function of zeolite on the nucleation had no direct relation with its own crystal lattice and its cell parameters.
21-P-10 - Synthesis and characterization of SnO2 nano particles in zeolite hosts Yi. Zhang, Xi. Wang and Xu. Wang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116012, China, [email protected]. Zeolite-entrapped SnO2 nano-semiconductor was synthesized by microwave ion-exchange method and chemical vapor deposition (CVD). The materials were studied by XRD, UV-Vis, FS and l l9Sn MAS NMR. Sn(IV) can be effectively introduced into the channels of zeolite hosts by microwave ion-exchange method. The hydration of Sn(IV) with H20 can be lessened under microwave irradiation, which improves the incorporation of Sn(IV) ions into the channels of the zeolites. For the CVD method, zeolite NH4Y is superior to NaY and HY as the host for SnO2 nano-semiconductor. The chemisorption of SnCI4 on the zeolite is correlated to the surface hydroxyl. SnO2 entrapped in zeolite has obvious quantum size effect. The materials also have excellent gas sensing properties in detecting ethanol.
21-P-11 - Encapsulation different routes
of Mn(bipy)2 into the zeolite Y prepared
via
B. Fan, W. Cheng and R. Li*
Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P.R. China. E-mail. rfii@tyut, edu. cn A series of zeolite Y, post-treated with various acids, synthesized in the organic-aminecontaining system, exchanged with Mn 2§ and prepared by direct addition of Mn(II) chloride in the crystallized mixture of zeolite Y, are used as hosts for the encapsulation of Mn(bipy)2. XRD, SEM, DTA, FTIR, and DRS measurements show that by flexible ligand method Mn(bipy)2 can be effectively encapsulated in different hosts. The properties of the hosts strongly influence the thermal stability and catalytic performances of encapsulated Mn(bipy)2. Upon treatment of zeolite Y with acids and the use of Mn-containing Y and Y synthesized in the system containing large-molecule organic amine as hosts, the catalytic activity can be significantly increased.
298
21-P-12 - Preparation of zeolite Beta/polystyrene beads and the corresponding hollow spheres V. Valtchev and S. Sferdjella
Laboratoire de Mat~riaux Min~raux, U.P.R.E.S.-A-CNRS 7016, ENSCMu, Universitd de Haute Alsace, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France Zeolite shells on polystyrene beads were prepared by a combination of layer-by-layer (LbL) and hydrothermal synthesis techniques. The negatively charged polystyrene beads were surface modified in order to adsorb zeolite Beta nanocrystals. Such particles were then adsorbed on the surface of the beads and induced to grow into a continuous film of intergrown crystals of zeolite Beta. The effect of the preliminary treatment on the formation of the zeolite film was studied. Finally the polystyrene beads used as macro-templates were removed by calcination in air, yielding hollow spheres of zeolite Beta. The zeolite Beta/polystyrene composites and the corresponding hollow zeolite spheres were characterized by XRD, SEM, TG/DTA and BET surface area measurements.
21-P-13 - Synthesis, characterization and catalysis of manganese(II) complexes encapsulated in NaX and NaY zeolites J.M. Silva (a), R. Ferreira (b), C. Freire (b), B. de Castro (b)and J.L. Figueiredo (a)
a Faculdade de Engenharia da Univ. Porto, [email protected] b CEQUP, Faculdade de Ci~ncias da Universidade do Porto, Portugal. The encapsulation of manganese(II)salen complexes into the pores of synthetic zeolites (NaX and NaY) was evaluated by different techniques: ICP-AES, XPS and SEM, TG-DSC, N2 adsorption, FTIR, UV-Vis. The results are consistent with the location of Mn complexes inside the micropores; even at low loadings it was possible to confirm this evidence. Catalytic tests in olefin epoxidation proved the existence of catalytic activity and the stereoselectivity of the complex after encapsulation. These catalytic results indicate that Mn-salen-zeolites may be promising heterogeneous catalytic systems.
21-P-14 - Guest-host interactions in systems containing liquid crystals confined to molecular sieves S. Frunza(a), L. Frunza(a,b), A. Sch6nhals(c), H.-L. Zubowa(b), H. Kosslick(b) and R. Fricke(b)
~National Institute of Materials Physics, Bucharest, [email protected], Romania bInstitute of Applied Chemistry, Berlin-Adlershof Germany ~Bundesanstalt far Materialforschung und Prafung, Berlin-Dahlem, Germany 4-Pentyl-4'-cyanobiphenyl and 4-octyl-4'-cyanobiphenyl liquid crystals (LCs) confined in molecular sieves of MCM-41 and cloverite types are studied in a wide temperature range by dielectric spectroscopy, thermal analysis and in-situ FTIR spectroscopy. The phase transitions of the bulk LCs cannot be detected when confined in MCM-41 sieve. A relaxational process occurs due to the molecular motions in the layer at the pore walls; the temperature dependence of the characteristic frequency obeys a Vogel-Fulcher-Tamman law associated to a glassy state. In the cloverite cages, the LCs keep the phase transitions of the bulk but shifted. Interactions between Lewis and BrOnsted sites and the LC molecules are monitored by IR spectroscopy. DTA measurements put also in evidence strong guest-host interactions.
299
2 1 - P - 1 5 - Zeolite Beta ordered macroporous structures with improved mechanical strength and controlled mesoporosity V. Valtchev, S. Sferdjella and H. Kessler Laboratoire de Matdriaux Min&aux, U.P.R.E.S.-A-CNRS 7016, ENSCMu, Universit~ de Haute Alsace, 3, rue Alfred Werner, 68093 Mulhouse Cedex, France Macroporous zeolite Beta structures were prepared by a self-assembly of monodisperse polystyrene spheres and zeolite nanocrystals followed by a hydrothermal treatment. The characteristic features of the self-assembled and hydrothermally treated macroporous structures were studied by XRD, FTIR, SEM, TG/DTA and nitrogen adsorption measurements. The hydrothermal treatment of the self-assembled composites led to intergrowth and closing of the mesopores between the nanocrystals building the walls of macropores. The mechanical properties of the macroporous zeolite structures were substantially improved by the secondary growth of the zeolite crystals.
21-P-16 - Synthesis of zeolites with organic lattice K. Yamamoto (a), Y. Takahashi (b) and T. Tatsumi (b) a The University of Tokyo, Tokyo, Japan. b Yokohama National University, Yokohama, [email protected], Japan. Organic-inorganic hybrid zeolites with organic lattice were successfully synthesized by using organically bridged silane as a silica source. 29Si and 13C MAS NMR spectra and IR spectra proved the presence of organic lattice (Si-CH2-Si) partially replacing siloxane bond (Si-O-Si), although some of Si-C bonds were cleaved. Their unit cell sizes were slightly larger than those of their completely inorganic counterparts presumably due to the longer bond length of Si-C than that of Si-O. When synthesized in the absence of organic template molecules, they showed microporosity like ordinary zeolites. This is the first example of the successful synthesis of zeolites having an organic group as lattice in a strict meaning.
2 I-P-17 - Crystallization mechanism of AIMepO-13 Y. Qi, G. Wang and Z. Liu Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P.O. Box 110, Dalian 116023, China, [email protected] A microporous aluminum methylphosphonate, A1MepO-[3, was prepared by hydrothermal method. The crystallization process was studied using XRD, PC-NMR, IR and SEM. It was found that phase transformation occurred in the crystallization process. There is an intermediate phase (nominated Phase A) between the starting gel and A1MepO-13. A1MepO-13 is not stable in the crystallization condition, and apt to be converted to more stable products A1MepO-~ and amorphous phase. The scheme for the crystallization process is suggested as: staring material ~ Phase A --~ A1MepO-13 --+ A1MepO-~ + amorphous phase.
300
21-P-18- Crystal structure and magnetic properties of rubidium clusters in zeolite L T A T. Ikeda a and T. Kodaira b aNational Institute for Research in Inorganic Materials, 1-1, Tsukuba, 305-0044, Japan bNational Institute of Materials and Chemical Research, 1-1, Tsukuba, 305-8565, Japan The Rb metal-doped Rb-type LTA shows an interesting magnetic property whose magnetic susceptibility obeys the Curie-Weiss law with a negative Weiss temperature. Rb atoms can be loaded up to 5.4 atoms per Gt-cage. The crystal structure of the Rb loaded Rb-type LTA is determined using X-ray powder diffraction under ultrahigh vacuum conditions. By increasing the loaded density of the Rb cluster, arrangements of the Rb + ions in adjacent m-cages went from equivalent to nonequivalent and the local symmetry for framework was degraded from Oh to Yd. The structural arrangement is clearly revealed by electron density distribution using the maximum entropy method. The magnetic property, which can be interpreted by the Dzialoshinsky-Moriya (DM) interaction, is strongly related to the noncentrosymmetric arrangement of the Rb clusters.
301
26 - Catalysis for Oil Refining (Wednesday) 26-P-06 - Hydroisomerization of n-decane in the presence of sulfur. Effect of m e t a l - a c i d balance and metal location L.B. Galperin, S.A. Bradley and T.M. Mezza UOP LLC, P.O. Box 5016, Des Plaines, Illinois, USA,"[email protected] Isomerization of n-decane in the presence of 1000 ppm H2S was studied on bifunctional PtMAPSO-3! catalysts. Sulfur suppresses the catalyst metal function, thereby changing the metal-acid balance which is required for high performance. Methods for controlling the catalyst metal-acid balance by changing the ratio between metal and acid functions are demonstrated. Catalysts with high isomerization selectivity in the presence of sulfur should have a strong metal function. Close proximity of metal and acid sites, as well as highly dispersed metal located on the binder, gives a catalyst with an isomerization selectivity of about 90%. This is similar to selectivity of the same catalyst in the absence of sulfur.
2 6 - P - 0 7 - Hydrodesulfurization of benzothiophene supported on mesoporous silica MCM-41
over noble metals
M. Sugioka(a), A. Seino(a),T. Aizawa(a), J.K.A. Dapaah(a), Y. Uemichi(a) and S. Namba(b) a Muroran Institute of Technology, Muroran, [email protected], Japan bTeikyo University of Science and Technology, Yamanashi, Japan It was found that the Pt/MCM-41 catalyst showed high and stable catalytic activity for the hydrodesulfurization of benzothiophene at 350 ~ and this activity was higher than that of commercial CoMo/A1203 catalyst. The Pt/MCM-41 catalyst has high sulfur-tolerant property towards hydrogen sulfide formed in hydrodesulfurization of benzothiophene. The silanol group (Si-OH) of MCM-41 and the spillover hydrogen formed on Pt particle in Pt/MCM-41 catalyst play important roles in the hydrodesulfurization of benzothiophene. Pt/MCM-41 might be a promising new hydrodesulfurization catalyst for bulky organic sulfur compounds in the petroleum feedstocks.
26-P-08 - Catalytic functionalities of USY zeolite supported hydrotreating catalysts K.S. Rawat, M.S. Rana and G. Murali Dhar* Indian Institute of Petroleum, Dehradun, INDIA - [email protected] USY zeolites of varying Si/A1 ratios were used as support for Mo, NiMo, CoMo and NiW catalysts. Both the effect of variation of Si/A1 ratio of the zeolite and Mo content on support at fixed Si/A1 ratio were studied. The catalysts were examined by XRD, oxygen chemisorption and TPR techniques. The hydrodesulfurization and hydrogenation reaction studies indicated that these catalysts are more active than y-A1203 supported catalysts and the increase in activities may be attributed to an increase in Mo dispersion and reducibility. It was found that oxygen uptake correlates well with the catalytic activity.
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2 6 - P - 0 9 - Highly active, selective and stable ferrierite-based catalysts for the skeletal isomerization of n-C5-C7 C.P. Nicolaides a, J. Makkonen b and M. Tiitta b Chemical Process Engineering Research Institute, National Centre for Research and Technology - Hellas, Thermi- Thessaloniki - cnicolai@alexandros, cperi, certh, gr, Greece; 6Fortum Oil and Gas, Oil Research and Development, Porvoo - [email protected], Finland Various ferrierite zeolites prepared via different synthetic routes were tested as catalysts for the skeletal isomerization of n-Cs-C7 olefins. The ferrierite samples having a small particle size, low total aluminum content, but a high percentage of aluminum in framework positions, showed the highest activity and selectivity for the reaction and stable catalytic performance with time-on-stream.
26-P-10 - Producing synthetic steamcracker feed from cycloalkanes (or aromatics) on various zeolite catalysts A. Raichle, H. Scharl, Y. Traa and J. Weitkamp Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany, jens. weitkamp@po, uni-stuttgart, de Methylcyclohexane (which can be readily manufactured from toluene by conventional ring hydrogenation) is converted into a high-quality steamcracker feed over the acidic zeolites HY, H-Beta, H-ZSM-11, H-ZSM-5, H-ZSM-22 and H-ZSM-35, thereby opening a new route for the utilization of surplus aromatics. While the conversion decreases with increasing geometrical constraints, the selectivity to the desired C2+-n-alkanes (mainly ethane, propane and n-butane) shows the opposite behavior. This is attributed to a higher contribution of Haag-Dessau cracking on zeolites with narrow pores.
26-P-11 - n-Heptane hydroconversion and methylcyclohexane cracking as model reactions to investigate the pore topology of NU-88 zeolite S. Lacombe, A. Patrigeon and E. Benazzi IFP, Rueil-Malmaison Cedex, France - [email protected]. The n-heptane hydroconversion is a useful and simple tool to get primary ideas on the pore topology of new zeolites, although a more precise investigation requires the use of more complex molecules. This model reaction was used to investigate the pore topology of NU-88 zeolite. By working on the rate of appearance of the products and on the composition of the isomers and cracked products, it could be proposed that NU-88 zeolite contains 10 MR channels with large intemal void spaces, which could be intersections of 10 MR channels or extra-cavities. The results were complemented with a methycyclohexane cracking test, where the importance of hydrogen transfer reactions confirms the presence of large cavities.
303
26-P-12 - New Mo and NiMo hydrodesulfurization catalysts supported on AI-MCM-41. Effect of the support Si/A! molar ratio T. Klimova, M. Calder6n and J. Ramirez
Departamento de Ingenieria Quimica, Facultad de Quimica, Universidad Nacional Aut6noma de M~xico, Cd. Universitaria, M~xico D.F. [email protected], M~xico A series of Mo and NiMo catalysts supported on Al-containing MCM-41 was prepared and characterized. It was shown that the incorporation of A1 atoms into the siliceous MCM-41 framework causes a deterioration of the textural characteristics and some loss in the periodicity of the MCM-41 pore structure. However, the acidity of the Al-containing MCM41 is substantially higher. The dispersion of Mo and Ni oxidic species increases with the incorporation of aluminum in the MCM-41 support, that produces an increase in the total conversion of dibenzothiophene. It was found that this effect is due to the interaction of Mo and Ni oxidic species with aluminum atoms of the MCM-41 support.
2 6 - P - 1 3 - Hydrogenation and ring opening of mono- and diaromatics for Diesel upgrading on Pt/Beta catalysts M.A. Arribas, J.J. Mahiques and A. Martinez
Instituto de Tecnologia Quimica, UP V-CSIC, Valencia, amart@itq, upv. es, Spain The combined hydrogenation and ring-opening of tetralin and 1-methylnaphthalene has been carried out on bifunctional Pt/Beta catalysts. The influence of the acidic and textural properties of the zeolite on activity and selectivity has been studied by varying the zeolite crystal size and the Si/A1 ratio by means of acid and steaming treatments. Similar trends were found for both aromatic reactants. Selectivity to products with the same number of carbon atoms than the feed and yield to ring-opening products increased while decreasing the BrOnsted acidity of the zeolite and by decreasing the size of the crystallites. Better catalytic performance was obtained for the catalyst prepared from a Beta zeolite dealuminated by steaming thus having a higher mesoporosity and reduced acidity.
26-P-14 - Hydro denitrogenation activity of N i O supported on various mesoporous alumino silicates
MoO3
catalysts
K. Shanthi, N.R. Sasi Rekha, R. Moheswari and T. Sivakumar
Department of Chemistry, Anna University, Chennai, India. Mesoporous alumino silicate molecular sieves with MCM-41 type structure synthesized using various A1 sources (i.e.: aluminum sulphate, aluminum isopropoxide, pseudo boehomite and sodium aluminate) have been used as supports for N i - Mo catalysts. The HDN of o-toluidine and cyclohexylamine was studied in a fixed bed flow reactor at 450~ and PH2 = 1 atm. The activity per unit of weight of the M C M - 41 supported catalysts was evaluated and compared to that of supported catalysts prepared by sequential impregnation method. The XRD and DRS data have been used to explain the observed trend in catalytic activity towards HDN reaction
304
26-P-15 - Model hydrocracking catalysts combining NiMo sulfide and large-pore zeolite" effect of the zeolite nature on the location of NiMo sulfide in relation with catalytic properties J. Leglise (a), D. Cornet (a), M. Ba~lala (a), C. Potvin (b) and J.-M. Manoli (b) a Catalyse et Spectrochimie, ISMRA, Caen - [email protected]. b Rdactivitd de Surface, Universitd P. & M. Curie, Paris- [email protected] Ni and Mo ions were deposited into HBEA and HY zeolites, then sulfided. The solids were characterized at all preparation stages by various methods, notably by MAS-NMR, FT-IR, and TEM-EDX. The catalytic bifunctional properties were determined in the hydroconversion of benzene (8 MPa H2, 1 h"l, 240-360~ With both zeolites, about half of the Ni-Mo is located in cavities and mesopores, but the internal NiMo is better sulfided with the nanocrystalline BEA zeolite. Catalyst NiMoS/BEA was much more active and slightly more selective for hydrogenation than NiMoS/Y.
26-P-16 - Effect of zeolite acidity characteristics on the deactivation behavior of bifunctional large-pore zeolite catalysts during cyclopentane hydroconversion S. Gopal and P.G. Smirniotis Department of Chemical Engineering, University of Cincinnati, Cincinnati, USA Panagiotis. Smirniotis@uc. edu Time stability of Pt loaded zeolite Y, beta, mordenite and ZSM-12 was investigated at several different Si/AI ratios using cyclopentane as a coke producing agent. Although zeolite pore structure determined coking resistance to a large extent, significant differences in catalytic performance were observed within a particular type of zeolite depending on the Si/A1 ratio. This could be explained based on acid site density as it not only decreased the coking severity but also controlled metal dispersion and metal acidity balance in the catalyst. In general zeolites with Si/AI ratios between 15 and 40 showed the best stabilities in this study.
26-P-17 - Characterization and catalytic activities of MCM-41 supported WS2 hydrotreating catalysts T. Chiranjeevi, P. Kumar, M.S. Rana, G. Murali Dhar and T.S.R. Prasada Rao Catalysis Division, Indian Institute of Petroleum, Dehradun,, INDIA WO3-MCM-41 catalysts were prepared with good dispersion of WO3. The oxygen chemisorption in the sulfided state indicated that WS2 is also well dispersed on MCM-41 surface. 02 chemisorption as a function of W loading indicated that maximum dispersion and maximum number of anion vacancies are obtained with 19wt% W with highest catalytic activities for HDS, HYD, HDO. The small crystallite size and its constancy as function of W loading coupled with low surface coverage by WS2 indicated that monolayer WS2 patches are formed on the selected regions of support surface. The correlation between 02 uptake and catalytic activity indicated that oxygen chemisorption is not specific to any of the functionalities of the overall dispersion of WS2. Co and Ni addition resulted in promotional effect for both HYD and HDS; it is suggested that the three catalytic functionalities originate from different set of sites on the WS2 and its promoted analogues.
305
26-P-18 - Isomerization and hydrocracking of n-heptane and n-decane over bifunctional mesoporous molecular sieves C. Bischof and M. Hartmann
Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany, hartmann@rhrk, uni-kl,de n-Heptane and n-decane hydroconversion have been investigated on platinum-, palladiumand ruthenium-containing A1MCM-41 (nsi/nal = 23) mesoporous molecular sieves. High selectivities for branched isomers have been observed on 0.27 Pd/HAIMCM-41 at reaction temperatures ranging from 250 to 380~ The product distribution is comparable with the one found for ideal bifunctional catalysis. While on 0.27 Pd/HAIMCM-41 no cracking on the metal function (hydrogenolysis) was observed, the cracked product distribution found on 0.5 Pt/HA1MCM-41 indicates that hydrogenolysis also occurs. Over 0.26 Ru/HAIMCM-41, the high yields of methane, ethane and linear hydrocarbons reveal a high hydrogenolysis activity of the ruthenium metal supported on AIMCM-41.
26-P-19 - Isomerization of cyclohexane, n-hexane and their mixtures on zeolite catalyst A. Holl6 (a*), J. Hancs6k (a) and D. Kall6 (b)
a University of Veszpr~m, Veszpr~m, [email protected], Hungary. b Chemical Research Center, Hung. Acad. of Sci., Budapest, [email protected], Hungary *Present address." Hungarian Oil and Gas Co., Sz6zhalombatta, [email protected], Hungary Isomerization of c-C6, n-C6 and their mixtures has been investigated on Pt/H-MOR. The effects of reaction conditions and feed composition on the yield of isomers, as well as on the composition of cracked and other products were examined. Rate equations and parameters involved were determined for the isomerization of pure alkanes and their mixtures. Isomerization rate equation can be derived assuming rate determining skeletal rearrangement, while in mixtures and at higher pressures the transport in micropores seems to control the transformation.
2 6 - P - 2 0 - Application of adsorption Dubinin-Radushkevich equation for study of n-pentane and m-xylene conversion catalysts microporous structure S.B. Agayeva, B.A. Dadashev, S.I. Abasov and D.B. Tagiyev
Institute of Petrochemical Processes, Azerbaijan Academy of Sciences 30, N.Rafiev st., 370025, Baku, Azerbaijan, E-mail." [email protected], [email protected] The adsorptive and catalytic properties of zeolites HY, HZSM-5 and HM (natural and synthetic) subjected to dealumination, ion exchange with rare-earth and transition elements have been studied.The changes in conversion and selectivity for m-xylene and n-pentane are shown to be connected with the changes of the zeolites microporous structure.These changes are in conformity with DR equation parameters. The DR equation could be applied to the simple test method elaboration of the starting and modified zeolites microporous structure through their adsorptive properties.
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26-P-21 - Hydroisomerization of n-hexadecane catalysts: Two different AI incorporation methods
over
Pt/AI-MCM-41
K.-C. Park and S.-K. Ihm
Dept. of Chem. Eng., KAIST, Taejon, skihm@_mai!.kaist.ac.kr, Korea. The hydroisomerization of n-hexadecane was carried out over Pt/A1-MCM-41 catalysts at 350~ and 103 bar. A1-MCM-41 was prepared by two different methods; a direct sol-gel method (Pre) and a post-grafting method (Post). A1-MCM-41 was characterized by using XRD, nitrogen adsorption, 27A1 NMR and ammonia TPD. The higher the amount of acid sites was, the higher the reactivity and isomer yield were. Pt/A1-MCM-41-Post showed higher conversions and higher isomerization yield than Pt/A1-MCM-41-Pre. Reaction results did not agree with A1-NMR data but with ammonia TPD. This difference was attributed to the better accessibility of tetrahedral sites (Broensted acid sites) in AI-MCM41-Post than those in A1-MCM-41-Pre.
26-P-22 - Zr-containing hexagonal mesoporous silicas as supports for hydrotreating catalysts N.G. Kostova, A.A. Spojakina, L.A. Petrov, O. Solcova a and K. Jiratova a
Institute of Catalysis, Bulgarian Academy of Science, Sofia, Bulgaria - [email protected]; alnstitute of Chemical Process Fundamentals, Acad. Sci. czech Republic, Prague This work reports the preparation of new supports for Mo- and NiMo-hydrotreating catalysts. Zr-containing mesoporous silicas with Zr/Si ratio from 0 up to 0.04 were prepared using TEOS, ZrOC102 and dodecylamine as a template. The materials and those modified with 12 % wt. Mo from 12-phosphomolybdic acid (HPMo) and its nickel salt were characterised by IR, TPD of NH3, TPR and their activities were measured in thiophene HDS. Activities in HDS of thiophene of Mo-containing catalysts prepared with the mesoporous silicas were higher than those of the catalysts prepared with amorphous silica.
26-P-23 - New catalysts for isomerization of long-chain n-paraffins M.I. Levinbuk,1 L.M. Kustov,2 T.V. Vasina,2 O.V. Masloboishchikova,2 M.L. Pavlov,3 I.E. Gorbatkina 4 and V.A. Khavkin 4
1Moscow Oil and Gas University, 65 Leninsky prospect, 1117917 Moscow, Russia 2N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia 3Salavat Catalyst Factory, Salavat, 4 Moscow Research Institute of Oil Refining, Russia Novel Y-type zeolite-based catalysts for isomerization of long-chain paraffins (nCT-nCl6) and aromatics hydrogenation have been developed. They provide high selectivity to isomerate with minimal feed cracking. Isomerization of nC7 is accompanied by benzene hydrogenation into methylcyclopentane and cyclohexane. Each reaction occurs on different sites and proceeds without altering the other one. The effect of the ratio of iso to n paraffins in gasoline fraction (IBP-62~ and 100-130~ was studied. Altenative methods to use the new catalysts in oil processing have been considered.
307
2 8 - Confinement and Physical Chemistry for Catalysis (Wednesday) 28-P-06- Use of coke-selectivated H-ZSM-5 in xylene isomerization F. Bauer and A. Freyer
Institut fi~r Oberfli~chenmodifizierung, 5, Leipzig, Germany- fbauer@rz, uni-leipzig.de The deposition of carbonaceous residues is used as modifying technique for the selectivation of H-ZSM-5 during xylene isomerization. An enhanced selectivity and a reduction of xylene loss was achieved by a thermal treatment of coke-selectivated H-ZSM-5 with hydrogen and propane. In the presence of these reactive carrier gases internal coke may be effectively removed and the remaining external coke covers those acid sites located on the crystallite surface which are responsible for undesired transalkylation and secondary isomerization reactions. Compared with samples selectivated with the xylene feed under high severity conditions deposits of about 0.3 wt.-% modified pre-coke using methanol as coke precursor are sufficient to reduce the xylene loss to 1.1% while maintaining the desired activity for ethylbenzene conversion of about 55 %.
2 8 - P - 0 7 - Photocatalytic reactions on chromium containing mesoporous molecular sieves under visible light irradiation: Decomposition of NO and partial oxidation of propane H. Yamashita*, K. Yoshizawa, M. Ariyuki, S. Higashimoto, and M. Anpo*
Osaka Prefecture University, yamashita@chem, osakafu-u, ac,/p, Japan The photocatalytic reactivities of Cr-containing mesoporous molecular sieves (Cr-HMS) have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O. In the presence of NO, Cr-HMS exhibited photocatalytic reactivity for the decomposition of NO into N2, 02, and N20 not only under UV light irradiation but also visible light irradiation. Especially, under visible light irradiation, a higher selectivity for N2 formation was observed. In the presence of propane and 02, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein with a high selectivity, while a complete oxidation proceeded under UV irradiation mainly to produce CO2. The charge transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactivities.
28-P-08 - Enhancing the shape selectivity of nanocrystalline HZSM-5 zeolite via comprehensive modifications H..C. Guo, X.S. Wang and G.R. Wang
Institute of Industrial Catalysis & State Key Lab. of Fine Chemicals, Dalian Universityof Technolog)4, Dalian, P R. China- [email protected] Fine tuning of a nano-HZSM-5 (20-50 nm, S I O 2 / A 1 2 0 3 = 25) was achieved by systematic modifications. Evaluations were made through analyzing zeolitic overall acid strength, external surface acid sites and microporous geometric constraints and the shape-selectivity in ethylbenzene ethylation. It is concluded that nano-ZSM-5 can be trimmed into highly shapeselective catalyst by exploiting the synergic effect of zeolitic overall acid strength suppression, microporous geometric constraints regulation and external acid sites passivation.
308
28-P-09 - Nature of shape-selective catalysis in the ethylation and the isopropylation of biphenyl over H - m o r d e n i t e s Y. Sugi a*, S. Tawada a, T. Sugimura a, Y. Imada a, Y. Kubota a, T. Hanaoka b and T. Matsuzaki b a Department of Chemistry, Gifu University, [email protected], Japan b National Institutes of Materials and Chemical Research, Tsukuba 305-8565, Japan 4-Isopropylbiphenyl (4-IPBP) was consumed much faster than 3-IPBP in their competitive isopropylation. Selectivity for 4,4'-diisopropylbiphenyl (4,4'-DIPB) in bulk products decreased with the increase of 3-IPBP, however, the selectivity in encapsulated products kept constant. 4-Ethylbiphenyl (4-EBP) disappeared much faster than 3-EBP in their competitive ethylation. Selectivity for 4,4'-diethylboiphenyl (4,4'-DEBP) was less than 2 %, whereas total selectivity for DEBPs with 4-ethyl group was higher than 65 % in both products: DEBPs were predominantly produced from 4-EBP. HM-pores were too loose to form 4,4'-DEBP.
28-P-10 - A d s o r p t i o n of selected amino acids from a q u e o u s solutions on m e s o p o r o u s molecular sieves S. Ernst, M. Hartmann and S. Munsch Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany, sernst@rhrk, uni-kl, de The adsorption of various amino acids from aqueous solutions using MCM-41-type mesoporous molecular sieves is discussed on the basis of their adsorption isotherms. The amounts adsorbed strongly depend on the pH and the nature of the individual amino acid: Amino acids with acidic side chains are hardly adsorbed, whereas basic amino acids show very high affinities to the mesoporous adsorbent. The uptake of amino acids with non-polar side chains increases with the chain length. The adsorption complex is proposed to consist of the cationic form of the amino acid attached to the negatively charged silica surface.
28-P-11 - Influence of O H groups of Beta zeolites on the synthesis of M T B E F. Collignon a and G. Poncelet Universit~ Catholique de Louvain, Unit~ de Catalyse et Chimie des Mat~riaux Divis~s, Place Croix du Sud 2/17, B-1348 Louvain-la-Neuve, Belgium. a Katholieke Universiteit Leuven, Centrum voor Oppervlaktechemie en Katalyse, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium, [email protected] Vapor phase synthesis of MTBE over zeolite Beta is very efficient. For example, Beta zeolite is three times more active than Amberlyst-15 for MTBE vapor phase synthesis at 50~ The better catalytic performance of H-Beta was verified in liquid phase. The external surface area, the amount of bridging A1OHSi, and silanol groups are important zeolite parameters for the ether synthesis. The reaction occurs on bridging A1OHSi acid sites. The highest yields are reached for low SiOH/A1OHSi ratios where methanol clusters bonded to silanol groups allow accessibility of isobutene to the active AIOHSi groups.
309
28-P-12 - About a possibilities of effectiveness increasing of porous catalyst granules with controlled activity profile v . v . Andreev Dept. of Control and Informatics in Technical Systems, Chuvash State University, Moskovskii pr. 15, 428015 Cheboksary, Russia; [email protected] The possibilities of effectiveness increasing of the porous catalyst granules with controlled activity profile are considered. Optimal control by the chemical reaction proceeding on such catalyst granules under artificially created non-steady-state conditions allows to make their productivity higher, than under steady-state conditions. On the base of analysis of critical phenomena of multiplicity states form it is possible to reach of the more high productivity of porous catalyst granule with controlled activity profile in case of a catalytic reaction proceeding under non-steady-state conditions.
2 8 - P - 1 3 - Effects of channel structures of wide pore zeolites on m-cresol transformation F. L6pez a, L. Gonzdlez a, J.C. Herndndez a, A. Uzcdtegui a, F.E. Imbert a and G. Giannetto b a Laboratorio de Cin6tica y Cat6lisis, Grupo de Materiales Microporosos en Cat6lisis, Departamento de Quimica, Facultad de Ciencias, Universidad ale Los Andes, La Hechicera b M6rida 5101A. Venezuela. Fax." +58 74 401286, e-mail. [email protected] ; Facultad de Ingenieria, Universidad Central de Venezuela, Los Chaguaramos, Caracas Venezuela. The m-cresol transformation was carried out on wide pore zeolites (HFAU, HBEA, HMOR and HOFF). The activity follows the sequence HFAU > HBEA>> HMOR > HOFF. The order of the acid strength determined by TPD-NH3 was HMOR>HOFF>HBEA>HFAU. On the HBEA. HMOR and HOFF the isomerization was the main reaction due to their pore system structure, that limits the formation of diphenylmethane intermediate of disproportionation, while on HFAU the disproportionation reaction was not impeded at low conversion. The p/o selectivity is mainly function of conversion.
28-P-14 - A study on the use of zeolite Beta as solid acid catalyst in liquid and gas phase esterification reactions. The influence of the hydrophobicity of the catalyst M.J. Verhoef", R.M. Koster b, E. Poels b, A. Bliek b, J.A. Peters a and H. van Bekkum a aTechnische Universiteit Delft, H. [email protected], The Netherlands blnstituut voor Technische Chemic, Universiteit van Amsterdam, The Netherlands Zeolitic materials with Si to AI r a t i o s - with accent on zeolite B e t a - were tested in esterification reactions. Hydrophilic materials proved to be inactive in the liquid phase esterification of apolar substrates. This may be ascribed to strong adsorption of water formed. More polar substrates are able to compete with water for the adsorption sites; thus, the influence of the hydrophobicity of the catalyst on its activity becomes less pronounced. Such influence is negligible on the activity of the catalysts in gas phase reactions. Here, the activity is mainly dependent on the amount and the strength of acid sites.
310 2 8 - P - 1 5 - The influence of pore geometry on the alkylation of phenol with
methanol over zeolites G. Moon, K.P. M611er, W. B6hringer and C.T. O'Connor
Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, Rondebosch, South Africa - gmoon@chemeng, uct.ac.za The alkylation of phenol with methanol, in the liquid phase, has been investigated using zeolites H-ZSM-5, H-beta, H-MCM-22, H-mordenite, H-USY as well as amorphous silica alumina. At the low temperature of 200~ anisole was the major product over all the catalyst investigated, second was cresols. H-Beta, H-USY, H-ZSM-5, H-mordenite and amorphous silica alumina showed similar cresol distributions. H-MCM-22, which has the smallest pore openings and the narrowest channel system among all zeolites studied, showed the highest preference for p-cresol.
28-P-16 - Diffusion analysis of c u m e n e cracking over Z S M 5 using a jetioop reactor P. Schwan and K.P. M~ller
Department of Chemical Engineering, University of Cape Town, South Africa. Cumene is cracked in a recycle reactor over commercial H-ZSM5 extrudates during a pulse experiment. The results are compared to those obtained from steady state measurements. A linear model for diffusion, adsorption and reaction rate is applied to reactants and products. In contrast to literature it is shown that if the Thiele modulus is greater than 5, the system becomes over parameterised. If additionally adsorption dynamics are negligible or not measurable, only one lumped parameter can be extracted, which is the apparent reaction constant found from steady state experiments. The pulse experiment of cumene is strongly diffusion limited showing no adsorption dynamics of cumene. However, benzene adsorbed strongly on the zeolite and could be used to extract transient model parameters.
311 2 9 - New Approaches to Catalyst Preparation (Wednesday) 2 9 - P - 0 5 - Catalytic properties of MFI zincosilicates s. Kowalac, E. Szymkowiak, I. Lehmann and G. Giordano*
Faculty of Chemistry, A. Mickiewicz University, Poznati, Poland. *Department of Chemical Engineering, University of Calabria, Rende, Italy. skowalak@main:amu.edu.pl A series of zincosilicates MFI was synthesized from the mixtures of even Zn/Si ratio and various silicon sources. The properties of the resulting samples differed considerably regarding their zinc content, the crystallite morphology and size and catalytic activity. The samples modified with various cations (Ca, Cu, Zn, AI, H) showed some activity for 2-propanol dehydration (no acetone was detected). The samples modified with AI cations showed the highest activity. It is likely that part of A1 could attain the framework positions or facilitate a generation of separated acidic OH groups. The lower activity of the H-forms could result from the presence of hydrogen bonds between adjacent hydroxyls.
2 9 - P - 0 6 - Acidity characterization of dealuminated H-ZSM-5 zeolites by
isopropanol dehydration C.S. Triantafillidis, V.A. Tsiatouras, A.G. Vlessidis and N.P. Evmiridis*
University of loannina, 45 110 Ioannina, [email protected], Greece A series of dealuminated ZSM-5 zeolites with various framework Si/A1 ratios were prepared by different methods (HC1, ammonium hexafluorosilicate, steaming). The number of acid sites that correspond to the high-temperature desorption peak of the ammonia-TPD spectra of all the dealuminated samples is in 1:1 mole analogy to the framework A1 (FA1), irrespective the degree and the type of dealumination method. The catalytic activity of the H-ZSM-5 zeolites for isopropanol dehydration is linearly related to the number of acid sites that correspond to the FAl-content (Brtinsted acidity). The Si-A1 amorphous phase that is formed in the hightemperature steamed samples affects activity and induces different product selectivity for propene and diisopropyl ether.
2 9 - P - 0 7 - A c i d i c Z r O 2 / S O 4 2 in mesoporous materials Y. Sun, L. Zhu, H. Lu, D. Jiang, and F.-S. Xiao*
Key Laboratory of Inorganic Synthesis and Preparative Chemistry & Department of Chemistry, Jilin University, Changchun 130023, China,[email protected] ZrO2/SO42 supported in mesoporous hexagonal materials such as MCM-41 were prepared by dispersion of ZrOC12.8HzO into the mesopores, followed by the hydrolysis and sulfation. They have been characterized by X-ray diffraction, nitrogen adsorption isotherms, infrared spectroscopy, and catalytic cracking of cumene and 1,3,5-triisopropylbenzene. The results show that ZrO2/SO4 2" was successfully loaded into the inner pores of MCM-41 and the as-synthesized catalyst showed favorable catalytic properties. The factors in the preparative process that affected the final activity were discussed.
312
29-P-08- HMS catalysts containing transition metals or transition metal complexes z. Fu, D. Yin ,W. Zhao, Y. Chen, D. Yin, J. Guo, C. Xiong and Luxi Zhang Institute of Fine Catalysis and Synthesis, Hunan Normal University, Changsha, 410081, P R China Copper, titanium, cobalt and iron substituted mesoporous silicas (Cu-, Ti-, Co-, and Fe-HMS) were synthesized with dodecylamine surfactant as templating reagent. Three assembled pathways were used to bond Ti tartrate complex over mesoporous silicas (HMS). The above described catalysts were characterized by XRD and FT-IR, their metal loadings were measured by chemical analysis method. In catalytic testing, Cu-HMS and especially Fe-HMS show the best catalytic activity for hydroxylation of phenol with H202 in the presence of water. Ti-HMS and especially Ti tartrate complex assembled HMS catalysts exhibit the best epoxidative activity for catalyzing epoxidation of styrene with tert-butyl hydroperoxide.
29-P-09 - Synthesis of hydrophobic mesoporous molecular sieves by surface modification K.-K. Kang and H.-K. Rhee* School of Chemical Engineering and Institute of Chemical Processes Seoul National University, Seoul 151-742, [email protected], Korea AlkyI-MCM-41 was prepared by surface modification technique. The modification was conducted by chemically bonding an alkyl substituent to the surface of pure silica MCM-41 via an organic reaction. In this work methyl and butyl groups were successfully introduced to MCM-41.
29-P-10 - Guanidine catalysts supported on silica and micelle templated silicas" new basic catalysts for organic chemistry D.J. Macquarrie
313
29-P-11 - Texture of dealuminated mordenite catalysts modified with cerium and catalytic properties in the isopropylation of biphenyl M. Krfilik (a), J. Horniakova (a), D. Mravec (a), V. Jorik (a), M. Michvocik (a) and P. Moreau
a.Slovak University of Technology, Email." [email protected] b ENSCM, 8 rue de l 'Ecole Normale, 34296 Montpellier, Cedex 5, France Formation of dispersed phase of ceria in the dealuminated mordenites modified with ceria/cerium was registered by XRPD. Decrease in acidity at increased content of ceria may be prescribed to ion-exchange of protons with cerium cations. An extra mesoporous structure of ceria at higher metal loading (more than 10 wt. %) was found. On one side, a lower acidity and narrower channels of catalysts resulted in the lower catalytic activity, on the other side higher selectivity to the desired 4,4'-dialkylated biphenyl was achieved.
29-P-12 - Partially crystalline zeolitic material as novel solid acid catalysts M. Liu, Z. Li, S. Lou, Q. Wang and S. Xiang*
Department of Chemistry, Nankai University, Tianjin 300071, [email protected], P. R. China Samples of zeolite beta varying in XRD crystallinity were prepared and used to catalyze the reaction of methanol and isobutene to form MTBE (methyl tert-butyl ether). Considerable high catalytic activity and selectivity to MTBE were maintained over partially crystalline zeolite beta. The maximum conversion of isobutene over 30% crystalline sample was only slightly lower than that of fully crystalline one, but the selectivity to MTBE was much higher. It was evidenced further by TPDT method that the strong interaction between template and aluminosilicate had occurred at the early stage of crystallization, the presence of X-ray amorphous zeolitic species, the smaller crystallite and lowe~ Si/Ai ratio may account for the observed catalytic characteristics.
29-P-13 - Novel mesoporous carbon as a catalyst support for Pt and Pd for liquid phase hydrogenation reactions W.S. Ahn a* , K.I. Min,a Y.M. Chung,b H.-K. Rhee,b S.H. JooC and R. Ryoo ~
School of Chemical Science and Engineering, Inha University, Inchon, [email protected]; b School of Chemical Engineering and Institute of Chemical Processes, Seoul National University, Kwanak-ku, Seoul, Korea, ~Department of Chemistry, Korea Advanced Institute of Science and Technology, Taejon, Korea Pt and Pd supported on a novel mes0porous carbon with regular pore diameter of 3 nm was prepared, which showed significant improvement in liquid phase hydrogenation reactions.
314
29-P-14 - Investigation of catalytic activity of framework and extraframework cobalt and manganese in MeAPO-34 prepared from fluoride medium A. Ristid (a), G. Avgouropoulos (b), T. Ioannides (b) and V. Kau~i~ (a, c) a National Institute of Chemistry, LjubO'ana, [email protected], Slovenia b FORTH-ICE/HT, Patras, Greece c University ofLjubljana, Slovenia The surface acidity and catalytic activity of Co and Mg incorporated and impregnated in A1PO434 were examined with ammonia adsorption, temperature-programmed desorption (TPD) and with reaction of CO oxidation. Incorporation Of Co in the framework of A1PO4-34 leads to enhancement of surface acidity and to formation of strong acid sites, while in MnAPO-34 this effect is less pronounced. Samples with extraframework Co and Mg possess weak acid centres. CoAPO-34 is one to two orders of magnitude more active than Co/A1PO4-34, while Me/A1PO434 and MnAPO-34 are almost inactive in the reaction of CO oxidation.
2 9 - P - 1 5 - Preparation and characterization of bimetallic Pt-Zn catalysts supported on zeolite NaX J. Silvestre-Albero, F. Coloma, A. Sep61veda-Escribano and F. Rodriguez-Reinoso Departamento de Quimica Inorg6nica. Universidad de Alicante, [email protected], Spain. The effect of the zinc content and the reduction temperature on the characteristics and catalytic properties of bimetallic Pt-Zn catalysts supported on zeolite NaX have been analyzed. Catalysts have been characterized by TPR, XRD and XPS. Their catalytic behavior in the vapor phase hydrogenation of crotonaldehyde (2-butenal) was studied after reduction a 632 and 773 K. The presence of zinc causes a drastic decrease in catalytic activity, although the selectivity towards the hydrogenation of the C=O bond is improved. Higher reduction temperature also improves the catalytic selectivity. The formation of Pt-Zn alloyed phases upon reduction can explain this catalytic behavior, although the contribution of a steric effect due to constraints creation in the pores of the zeolite support can not be discarded. 29-P-16 - Surface modification of the uncalcined acid-made mesoporous silica
materials in a one-step procedure H.-P. Lin(a), Y.-H. Liu(b), C.-P. Kao(a), S.-B. Liu(a) and C.-Y. Mou(b)*
a Academia Sinica,, Taipei, Taiwan,, [email protected] b National Taiwan University, TaipeL Taiwan 106. [email protected] We investigate a new approach of surface functionalization of mesoporous silica. A direct template displacement method has been developed to graft silane ligands onto the surface of uncalcined mesoporous silica prepared from acidic condition. The organic surfactants can easily be recovered and re-used as the templates of the mesoporous silicas. The high density of surface silanol group in acid-synthesized silica leads to high loading of silanes. The mild reaction condition and short reaction time lead to the preservation of morphology.
315
29-P-17- Zirconia nanoparticles in ordered mesoporous material SBA-15 J. Sauer, S. Kaskel, M. Janicke and F. Schtith
Max-Planck-Institut fiir Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 M~ilheim an der Ruhr, Germany, [email protected] Zirconia particles were incorporated in the ordered mesoporous material SBA-15 by impregnating the calcined host material with zirconia precursor solutions and subsequent heat treatments. The materials were characterized by XRD, Nz-Sorption, TEM and EDX. Different analytical techniques indicate the incorporation of zirconia clusters inside the host structure with particle sizes between 3 and 5 nm, and the existence of a small amount of zirconia particles outside the host structure. According to the XRD pattern, the SBA-15 support stabilizes the tetragonal phase and the particle size up to a temperature of 1373 K. The materials were additionally sulfated by standard methods and showed in contrast to sulfated bulk zirconia a lower catalytic activity in the n-butane isomerization.
29-P-18 - Preparation using ozone treatment, characterization and application of isomorphously substituted Ti-, V- and Zr-MCM-41 catalysts D. M~hn a, J. Halfisz a, E. Meretei a, Z. Kdnya a, A. Fonseca b, J. B.Nagy b and I. Kiricsi a
Department of Applied and Environmental Chemistry, University of Szeged aRerrich tdr 1., H-6720 Szeged, Hungary, [email protected] bLaboratoire de RMN, Facultds Univer. Notre-Dame de la Paix, B-5000 Namur, Belgium Si-, Ti-, V- and Zr-MCM-41 catalyst samples were synthesized, and two different methods were used for removing the template from the as synthesized samples, either by the usual process at high tempereture in the presence of O2, or oxidation at 150 ~ with ozone. After the physical characterization (X-ray diffraction, 298i MAS NMR and IR spectroscopy, BET method) of the samples, oxidation of cyclohexane, cyclohexene and vinyl cyclohexene with H202 as test reactions were carried out. The catalytic activities and selectivities of the samples are different. It has been shown that the activity and selectivity of these modified MCM-41 catalysts in the oxidation reactions greatly depend on the method used for removing of template.
29-P-19- Preparation and catalytic evaluation of [Ga]MCM-58 and of MCM58-type catalysts with different aluminum contents S. Ernst, M. Hartmann, T. Hecht and A. Weber
Department of Chemistry, Chemical Technology, University of Kaiserslautern, Germany, sernst@rhrk, uni-kl, de The large pore zeolite MCM-58 has been synthesized with nsi/nAi-ratios varying from 15 to 35 and also in its new gallosilicate form [Ga]MCM-58 with a nsi/nca ratio of 15. The catalytic properties of these materials were characterized using the disproportionation of ethylbenzene and the hydroconversion of n-decane as catalytic tests. MCM-58 and Pt-loaded MCM-58, respectively, proved to be highly active catalysts in these reactions.
316
29-P-20- IR study on the reaction path of methanol decomposition over basic zeolites M. Rep (a), J.G. van Ommen (a), L. Lefferts (a) and J.A. Lercher (b)
a Faculty of Chemical Technology, University of Twente, Enschede, The Netherlands b Institutfiir Technische Chemic, Technische Universitcit Mfinchen, Garching, Germany Johannes. Lercher@ch. tum. de On the basis of an infrared study of the adsorption and reaction of methanol and dimethyl ether over alkali metal cation exchanged zeolites, we propose a reaction mechanism for the decomposition of methanol over alkali cation exchanged zeolites. Additionally, formaldehyde adsorption is performed on these molecular sieves and attempts will be made to correlate its adsorption structure with the surface reactivity.
29-P-21 - Synthesis and characterization of highly ordered mono- and bimetallic substituted MCM-41 molecular sieves and their catalytic properties in selective oxidation of hydrocarbons V. P~.rvulescu (a), C. D~.scalescu (a) and B.L. Su (b)
a Institute of Physical Chemistry, Bucharest, Romania; b The University of Namur (FUNDP), [email protected], Belgium. The mono- and bimetallic substituted MCM-41 catalysts with cobalt, vanadium or lanthanum have been prepared by direct synthesis or impregnation and characterized by various techniques, such as: XRD, Nz adsorption-desorption, SEM, TEM and TGA. The catalytic activity in the selective oxidation of styrene with H202 has been evaluated. Adsorption of benzene and ammonia on the mono- and bimetallic mesoporous molecular sieves with cobalt and vanadium has been studied by IR spectroscopy and the results have been correlated with their catalytic properties and the characteristics of the structure. Co-incorporated catalysts prepared by direct synthesis show to be very active and selective.
29-P-22 - On the direct synthesis of noble metal cluster containing MCM-41 using surfactant stabilised metal nanoparticles J.P.M. Niederer a, A.B.J. Arnolda,W.F. Hoelderich a, B. Spliethofb, B. Tesche b, M. Reetz b and H. Boenneman b
aUniversity of Technology R WTH Aachen, Germany- Hoelderich@R WTH-Aachen.de bMax-Planck-Institute for Coal Research, Muelheim, Germany [Me]x-MCM-41 containing nanosized particles of platinum, palladium, rhodium, ruthenium and iridium were directly synthesised from surfactant stabilised spherical metal nanoparticles in the synthesis gel, and characterised with XRD, ICP-AES, TG/DSC, TEM, nitrogen physisorption and carbonmonoxide chemisorption, and 29Si MAS NMR. During the synthesis some agglomeration of the particles took place, but the metal particles were present inside the pore system of MCM-41. The materials were active and selective catalysts in the hydrogenation of cyclic olefins such as cyclohexene, cyclooctene, cyclododecene and norbornene.
317
29-P-23 - M i c r o p o r o u s zincophosphates as solid base catalysts L.A. Garcia-Serranoa; T. Blascob; J. P6rez-Pariente a and E. Sastre a alnstituto de Cat6lisis y Petroleoquimica, C.S.I.C. - esastre@icp, csic. es, Madrid, Spain blnstituto de Tecnologia Quimica, UP V-CSIC, Valencia, Spain Samples of tridimensional microporous zinc phosphates with fully connected framework with structures type FAU and CZP have been prepared. The influence of some synthesis parameters on the nature of the crystalline phases obtained, such as crystallization time and temperature, concentration of the different reactives or pH, are discussed. Physicochemical characterization of the pure samples has been performed by different techniques: ICP, XRD, 13C and 31p MASNMR, TG, TG-MS, in-situ thermal XRD analysis and SEM. These materials were tested in the Knoevenagel condensation of different esters and benzaldehyde. They have demonstrated a good selectivity and a higher activity than the basic zeolites previously described in the literature with these reactions.
29-P-24 - Zirconium containing A I - M C M - 4 1 - synthesis, characterisation and catalytic p e r f o r m a n c e in 1-hexene isomerisation I. Eswaramoorthi a, V. Sundaramurthy a and N. Lingappan b aDepartment of Chemistry, Anna University, Chennai. India - [email protected]; bScience and Humanities Division, Madras Institute of Technology, Chennai. India Using the molar gel composition of SiO2:0.12 CTAB: x ZrO2: 0.01A1203: 0.19Na20: 35H20, where x = 0.02-0.04, zirconium containing AI-MCM-41 samples were synthesised and characterised by XRD, DRS, BET surface area, FT-IR and pyridine absorption studies. The increase of d-spaceing with increase of Zr content indicates the incorporation of Zr in the framework. In DRS, an absorption band around 210 nm confirms the presence of Zr (IV) in the tetrahedral co-ordination. The pyridine adsorbed FT-IR studies shows that the increasing incorporation of Zr in AI-MCM-41 increases the acidity of Zr-A1-MCM-41. Zirconium free AIMCM-41 and zirconium impregnated AI-MCM-41 show lower 1-hexene conversion and lower selectivity of skeletal isomerised products than that of Zr-A1-MCM-41 catalysts. This confirms the presence of Zr in the framework of MCM-41 and accounts for the increase in acidity.
29-P-25 - Iron containing zeolites and m e s o p o r o u s silica as sulfuric acid catalyst A. Wingen (a), W. Schmidt (a), F. SchOth (a), A.C. Wie (b), C.N. Liao (b) and K.J. Chao (b) (a) MPI fiir Kohlenforschung, Mfilheim, Germany, [email protected] (b) National Tsing-Hua University, Taiwan - kjchao@mx, nthu. edu. tw Iron modified zeolites and ordered mesoporous oxides have been studied as catalysts for the sulfur dioxide oxidation in sulfur rich gases. Both zeolitic materials and mesoporous oxides show very good activity in this reaction. Other than solid state or incipient wetness loaded MCM-41 materials, the zeolites do not show an initial loss of activity. However, they loose activity upon prolonged exposure to reaction conditions around 700~ The zeolitic samples were analyzed via X-ray absorption spectroscopy, and the deactivation could be related to removal of iron from framework sites to result in the formation of hematite-like species. If the iron can be stabilized in the framework, these materials could be an interesting alternative to other iron based catalysts for the commercial application in sulfur rich gases.
318
29-P-26 - Deep-bed dealumination of ZSM-5 zeolites. Changes in structure and catalytic activity P. Hudec, A. Smiegkovfi, Z. 2;idek, L. Sabo and B. Liptfikovfi
Department of Petroleum, Faculty of Chemical Technology, Slovak University of Technology, Radlinskdho 9, Bratislava, Slovak Republic- [email protected] Deep-bed dealumination of ZSM-5 zeolites with Si/A1 ratio of 15 and 21 at 560 and 780~ caused significantly changes in shape of adsorption isotherms t-plots. Low-pressure hystheresis loop on adsorption isotherms and corresponding two-linear region on t-plots indicate the framework dealumination to Si/Al>45. Total acidity of dealuminated samples was greater than expected on the base of Si/AI framework ratio, confirming significant role of EFAL as Lewis acid sites. TON of n-hexane cracking for deep-bed treated samples considerably increased, documenting synergetic effect of the action of protic and aprotic acid sites.
29-P-27 - Fabrication of honeycomb structures with powder MCM-48 silica Y.-S. Ahn (a), M.-H. Han (a), S. Jun (b) and R. Ryoo (b)
a Functional Materials Research Team, Korea Institute of Energy Research, Taejon, [email protected]; b Department of Chemistry (School of Molecular Science-BK21), Korea Advanced Institute of Science and Technology, Taejon, Korea Macroscopic honeycomb structures were fabricated with powder MCM-48 silicas by an extrusion process using bentonite or pseudobohemite as binder. The products were characterized by the X-ray diffraction patterns, specific BET surface areas and compressive strengths after sintered at temperatures as high as 750~ The fabrication process for MCM-48 has been investigated thereby. The result shows that stabilities of the raw MCM-48 materials are the bottleneck limiting the fabrication process. High-quality honeycombs retaining the wellordered mesoporous structure were obtained when MCM-48 was stabilized by the postsynthesis hydrothermal treatments before the fabrication. However, without the post-synthesis treatment, the MCM-48 structure was almost lost during the fabrication process.
29-P-28 - Acidic hybrid catalysts prepared by grafting large-pore silica M41S materials B. Lindlar (a), M. Ltichinger (a), M. Haouas (a), A. Kogelbauer (b) and R. Prins (a)
a Laboratory of Technical Chemistry, Swiss Federal Institute of Technology (ETH), prins@tech, chem. ethz. ch, Switzerland b Department of Chemical Engineering, Imperial College of STM, United Kingdom Large-pore mesoporous materials with enhanced textural characteristics (surface area, pore size distribution and pore volume) were obtained from a pH-adjusted synthesis with a surfactant mixture of hexadecyl- and dodecyltrimethylammonium salts in combination with mesityleneswelling. This material was grafted with phenyl-alkoxysilanes and subsequently sulphonated. Nitrogen adsorption and multinuclear MAS NMR were performed to monitor the different synthesis steps.
319
29-P-29 - Preparation of tungsten carbide supported on (AI-)FSM-16 and its catalytic activity M. Nagai, K. Kunieda, S. Izuhal and S. Omi
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, Japan - [email protected] The tungsten carbides on FSM-16 were prepared in carburizing of WO3/FSM-16 with 20% CH4/H2 and characterized using nitrogen adsorption, XRD, TEM, and NMR. The relationship between the surface properties and the catalytic activity of tungsten carbides on FSM-16 in cyclohexene hydrogenolysis at 250~ was discussed.
29-P-30 - Ti-MCM-48 with different titanium spectroscopic characterization and catalytic activity
loading:
synthesis,
V. Dellaroccaa; M.L. Pefiab; F. Reyb*; A. Cormab; S. Coluccia a and L. Marchese c aUniversitgt di Torino, Torino, Italy," bUniversidad Polit6cnica de Valencia, Spain. [email protected]; c Universith del Piamonte Orientale 'A. Avogadro ', Alessandria, Italy. A series of Ti-MCM-48 materials with different Ti contents has been synthesized and characterized in the as-prepared and calcined states. Also, the catalytic activity for the epoxidation of cyclohexene with tertbutylhydroperoxide on the different Ti-MCM-48 samples was tested. From this study, it has been possible to establishe the dispersion of Ti(IV) sites on the silica surface by means of DR-UV-Vis spectroscopy. These characterization results have been correlated with the final catalytic activity found for these mesoporous catalysts.
29-P-31 - Comparison of 3-aminopropyisilane linked to MCM-41 and HMS type silicas synthesised under biphasic and monophasic conditions D.J. Macquarrie,a M. Rocchia,b B. Onida,b E. Garrone,b P. Lentz,c J. B.Nagyc, D. Brunel d, A.C. Blanc d and F. Fajula d
~University of YORK, England. [email protected]; bPolitecnico di TORINO, Italy," CFacult~s Universitaires Notre Dame de la Paix, NAMUR, Belgium; dCNRS-ENSCM, MONTPELLIER, France. Functionalised mesoporous silicas prepared by either grafting by silylation of MCM-41 or by self-assembly co-condensation of organically functionalised silica precursors and silica precursor (RO)4Si in presence of non-ionic surfactants feature different properties. Materials were characterised by N2 sorption isotherms, FTIR and MAS-NMR. Imine formation during contacting the different samples with probes such as acetone and benzaldehyde demonstrated different environments of the anchored amine groups.
320
3 0 - E n v i r o n m e n t a l C a t a l y s i s (Wednesday) 3 0 - P - 0 6 - Effect o f the r e d u c t a n t n a t u r e on the catalytic r e m o v a l o f N 2 0 on a Fe-zeolite-beta catalyst G. Delahay (a), M. Mauvezin (a), B. Coq (a) and S. Kieger (b)
(a) Ecole Nationale de Chimie de Montpellier, [email protected], France. (b) Grande Paroisse, Paris-La D~fense, France A Fe(97)-BEA catalyst, prepared by conventional ion-exchange procedure and calcined at 773 K, almost contains iron-binuclear-oxo-species in charge compensation of the BEA structure. The re-oxidation of iron(II) species by N20 leads to new oxo-species reducible at lower temperature than the dimer species. Among H2, CO, propene and NH3 in the reduction of N20, CO, propene and NH3 are selective reductants. For these three reductants a similar light-off temperature of ca 638 K is obtained in the selective catalytic reduction of N20. It should be pointed out that CO is efficient from 473 K but its activity is limited by the reoxidation of Fe II to Fe III species by N20.
3 0 - P - 0 7 - D e g r a d a t i o n of N - n i t r o s a m i n e s on zeolites J.H. Zhu*, B. Shen, Y. Xu, J. Xue, L.L. Ma and Q.H. Xu
Department of Chemistry, Nanjing University, Nanjing 210093, China Degradation of N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) on zeolites was investigated by use of temperature programmed surface reaction and GC-MS. Activation of zeolite had almost no effect on TPSR of NPYR, because zeolite could selectively adsorb N-nitrosamines. Cyano derivative appeared as the main product on NaZSM-5 or NaY zeolites similar to that in pyrolysis while DNA became the dominant one on HZSM-5 or HY. On the latter the Br6nsted acid sites probably play the role of main catalytic sites, hence Nnitrosamines degrades to amines on BrOnsted acid sites while on the former N-nitrosamines might decompose through radical reaction process, similar as pyrolysis. No desorption of the N-nitrosamines occurs on zeolites even at elevated temperature, and protonation of zeolite
3 0 - P - 0 8 - Z r O 2 / N a Y : A n e w m a t e r i a l for r e m o v a l pollution J.H. Zhu*, J.R. Xia, Ying Wang, G. Xie, J. Xue and Y. Chun
of N - n i t r o s a m i n e s
Department of Chemistry, Nanjing University, Nanjing 210093, China Zirconia can be coated in NaY by microwave radiation and the content of ZrO2 was about 10 wt %. Loading ZrO2 generated some basic sites on the surface of zeolite NaY so that more Nnitrosopyrrolidine (NPYR) can be degraded at lower temperature than that on the parent zeolite. When the carrier gas in the degradation reaction was changed from nitrogen to air, the maximum concentration of NOx formed on ZrO2/NaY was dramatically decreased below 10 lamol/g though most of the N-nitrosamines were confirmed to be degraded instead adsorbed on ZrO2/NaY. Nitrogen is formed in degradation of NPYR as the main product over the ZrOa/NaY composite, resulting from the special catalytic function of dispersed ZrO2. With high activity for decomposition of N-nitrosamines and suppression for formation of NOx, ZrOz/NaY will be a functional material to remove N-nitrosamines pollution from environment.
321
3 0 - P - 0 9 - T o t a l oxidation of n-pentane, cyclohexane and their mixtures on the Cu-containing Z S M - 5 zeolites M.A. Botavina, N.V. Nekrasov and S.L. Kiperman
N.D.Zelinsky Institute of Organic Chemistry, Rus.Acad.Sci., Russia, [email protected] The kinetics of total oxidation of n-pentane, cyclohexane and their mixtures on Cu-containing ZSM-5 was studied to analyse possible effects of the critical size of reactant molecule on these processes. Oxidation of n-CsHl2 seems to proceed in kinetic region whereas C6H12 conversion is affected by intracrystalline diffusion of reactants. This conclusion is in a good accordance with hindrances for the mobility of investigated molecules. The oxidation of normal pentane takes place on all catalysts surface and its rate does not change in the presence of cyclohexane due to its low diffusivity, while cyclohexane conversion decreased significantly in the presence of normal pentane. This investigation has shown a fruitfulness of the kinetic approach to elucidation of diffusion effects in zeolite catalysis.
30-P-10 - Modified natural zeolite in catalytic clearing of exhaust and ejected gases from nitric and carbon oxides. L. Akhalbedashvili and S. Sidamonidze
Tbilisi State University, 380028, 3 Ave. Chavchavadze, e-mail: [email protected]., Tbilisi, Georgia A catalyst for joint conversion of nitric and carbon oxides was developed on the basis of natural zeolite-clinoptilolite from Georgian deposit. Catalyst making is accomplished with copper cations introduced by ion-exchange following previous decationation. The high activity in reduction of NO• by CH4, NH3, H2 and especially CO is explained by the presence of copper-ions in the zeolite structure. The conversiom degree of (NO• reaction reaches 95-98% above 400~ This catalyst has the following advantages: cheapness and availability of tuff, high zeolite content, simple making, low temperature of nitric and carbon oxides conversion (150-500~ possibility of regeneration.
30-P-11 - Selective catalytic reduction of N20 with light alkanes over different Fe-zeolite catalysts S. Kameoka(a), S. Tanaka(a), K. Kita(a), T. Nobukawa(a), S. Ito(a), T. Miyadera(b) and K. Kunimori(a)
a Institute of Materials Science, University ofTsukuba, [email protected], Japan. b National Institute for Resources and Environment, Tsukuba, Ibaraki, Japan Fe ion-exchanged zeolite catalysts (Fe-zeolite; Fe-BEA was the most active) perform effectively SCR of N20 with light alkanes (i.e., CH4, C2H6 and C3H8) even in the presence of excess oxygen. CH4 reacted selectively with N20 even in the presence of excess 02 (> 250 ~ 4N20 + CH4 ~ 4N2 + COz + 2H20), while the reaction of C2H6 and C3H8 with O2 was drastically enhanced by the presence of N20. It was found that N20 played an important role in the activation of alkanes at an initial step. On the basis of these results, we proposed a mechanism in the SCR of N20 with light alkanes over Fe-BEA catalyst.
322 3 0 - P - 1 2 - Selective catalytic reduction o f NOx by NH3 over Mn supported
MCM-41 mesoporous materials E.E. Iojoiu (a), P. Onu (a), S. Schmitzer (b) and W. Weisweiler (b)
a Technical University eGh.Asachb), Faculty of Industrial Chemistry, Bvd. D. Mangeron Nr. 71, 6600 lasi, Romania, [email protected], b University of Karlsruhe (TH), Institute of Chemical Technology, Kaiserstr. 12, D-76128 Karlsruhe, Germany Mn-MCM-41 catalysts were prepared and then tested using the selective catalytic reduction of NOx by NH3. The influence of the support (siliceous or aluminosilicate MCM-41) as well as the composition of the gas feed were investigated with respect to the catalytic activity. The pure siliceous MCM-41 seems to offer much better catalytic properties to the catalyst. The presence of a mixture of NO and NO2 in the gas feed causes an increase of SCR activity. The catalysts analysed exhibit fairly high NO• conversion at temperatures above 250~
30-P-13 - Transition metal exchanged-MCM-22 catalysts for N20 decomposition A.J.S. Mascarenhas (a), H.M.C. Andrade (b) and H.O. Pastore (a)
a Grupo de Peneiras Moleculares Micro- e Mesoporosas, Instituto de Quimica, Universidade Estadual de Campinas, lolly@iqm, unicamp, br, Campinas, Brazil. b Instituto de Quimica, Universidade Federal da Bahia, Salvador, Brazil. Transition metal exchanged-MCM-22 catalysts (Fe, Co and Cu) have shown high activity on the decomposition of nitrous oxide (N20), comparable to the well-known ZSM-5 catalysts. Cu-MCM-22 is highly active, but suffers inhibition by excess oxygen. Co-MCM-22 is not as active as Co-ZSM-5 due to the formation of CoO, but is nearly insensitive to 02. Fe-MCM22 presents an intermediate behavior, and shows low tolerance to oxygen. Activities and oxygen tolerance were explained on the basis of the nature of the active species formed in each case.
30-P-14 - The NO and N 2 0 selective catalytic reduction on copper and iron containing ZSM-5 catalysts: a comparative study G. Fierro, G. Ferraris, M. Inversi, M. Lo Jacono and G. Moretti
Centro CNR SACSO, c/o Dipartimento di Chimica, Universith "La Sapienza", Roma, giuseppe.fierro@uniroma l. it, Italy In this work we report a comparison between the activities of H-ZSM-5, H-[Fe]-ZSM-5, Cu-[Fe]-ZSM-5, Cu-ZSM-5 and Fe-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO and N20 by C3H8 in the presence of oxygen. The results show that for the NO reduction the order of activity is Cu-[Fe]-ZSM-5 ~ Cu-ZSM-5 > Fe-ZSM-5 > H-[Fe]-ZSM-5 H-ZSM-5. For the N20 reduction, the order of activity changed as follows: H-[Fe]-ZSM-5 > Fe-ZSM-5 > Cu-[Fe]-ZSM-5 -~ Cu-ZSM-5 > H-ZSM-5. Catalytic results for the N20 decomposition are also presented.
323
3 0 - P - 1 5 - A comparison of different preparation methods of indiummodified zeolites as catalysts for the selective reduction of NO C. Schmidt (a), T. Sowade (a), F.-W. Schtitze (b), H. Berndt (b) and W. Gr~inert (a)
aLehrstuhl Technische Chemie, Ruhr-Universitcit Bochum, Bochum, Germany blnstitut fiAr Angewandte Chemic Berlin-Adlershof e. V., Berlin, Germany The influence of the preparation method of In-modified zeolite catalysts for the SCR of NOx by methane on the structure of In species formed and the catalytic activity has been studied. The structure of the catalysts has been investigated by XPS, ISS, XAFS, FTIR, electron microscopy and TPR. Dependent on the preparation, indium may occupy zeolite cation sites or form intra- and extra-zeolite oxide aggregates. It was found that indium ions at cation sites provide a low-temperature SCR activity while clustered species are active at high temperatures.
30-P-16 - Local structures of Ag+/ZSM-5 catalysts and their photocatalytic reactivity for the decomposition of N20 into N2 and 02 M. Matsuoka, W.-S. Ju, and M. Anpo*
Department of Applied Chemistry, Graduate School of Engineering Osaka Prefecture University, anpo@ok, chem. osakafu-u.ac.jp, Japan Ag+/ZSM-5 catalysts were prepared by an ion-exchange method. In-situ characterization of Ag+/ZSM-5 catalysts by means of UV-Vis, photoluminescence and XAFS spectroscopies revealed that Ag § ions are anchored within the pore of ZSM-5 zeolite having a highly dispersed and isolated state. In-situ FT-IR and UV-Vis investigations showed that N20 molecules reversibly adsorb onto the isolated Ag+ ions to form Ag+-N20 complexes. UVirradiation of the Ag+/ZSM-5 catalysts in the presence of N20 led to the photocatalytic decomposition of N20 into N2 and 02 at 298 K. Investigations of the effective wavelengths of the irradiated light for the reaction revealed that the photoexcitation of the absorption band due to the Ag+-N20 complexes plays a significant role in this reaction.
30-P-17- One stage catalytic cracking of plastic waste on zeolitic catalysts K. Gobin, D. Koumantaropoulos and G. Manos
Department of ChemicaI Engineering, University College London, [email protected] The catalytic degradation of polyethylene to hydrocarbon fuel was studied over zeolites, US-Y, ZSM-5 and mixture of them (50% each), as well as zeolite-containing cracking catalysts. The presence of ZSM-5 increased the gas formation. The cracking catalysts were able to degrade polyethylene completely, resulting in high levels of yield to liquid products. The boiling point distributions of the liquid fractions formed over the cracking catalysts were similar to this formed over US-Y. The majority of the liquid products had boiling points below 500K, confirming the high quality of the liquid hydrocarbons produced by the method. The study has demonstrated the suitability of commercial cracking catalysts for the cracking of plastic waste and the potential of plastic waste to be co-fed into existing refinery FCC units.
324
30-P-18 - Analysis of the deep catalytic oxidation of binary C V O C s mixtures over H-ZSM-5 zeolite R. L6pez-Fonseca, J.I. Guti6rrez-Ortiz, A. Aranzabal and J.R. Gonzfilez-Velasco*
Department of Chemical Engineering, Faculty of Sciences, Universidad del Pais Vasco/EHU, P.O. Box 644, E-48080 Bilbao, Spain. E-mail." [email protected] The oxidative decomposition of binary mixtures of chlorinated VOCs (1,2-dichloroethane, dichloromethane and trichloroethylene) over H-ZSM-5 zeolite has been evaluated. The ease of destruction decreased in the order: DCE>DCM>TCE. The main oxidation products were CO, CO2, HC1 and C12. Some other chlorinated by-products were detected as well (vinyl chloride, methyl chloride and tetrachloroethylene). The destruction of chlorinated mixtures induced an inhibition of the oxidation of each CVOC. An important decrease in the formation of intermediates was noticed and HC1 selectivity was largely improved.
30-P-19 - Solid state MAS N M R studies of zeolites and alumina reacted with chlorofluorocarbons (CCI2F2, CHCIF2) I. Hannus (a), Z. K6nya (a), P. Lentz (b), J. B.Nagy (b) and I. Kiricsi (a)
a Department of Applied and Environmental Chemistry, University of Szeged, hannus@chem, u-szeged, hu, Hungary b Laboratoire de RMN, Facultds Universitaires Notre-Dame de la Paix, Belgium Multinuclear Magnetic Resonance of both the adsorbed and the solid phase allowed us to follow the reaction of various chlorofluorocarbons (CC12F2 and CHC1F2) on NaY, HZSM-5 zeolites and 7-A1203. The intermediates and the final products were identified by 13C and 19F NMR spectroscopy. At the same time the kinetics of the reactions could be determined at various temperatures. Over alumina dismutation reactions take place as primary steps caused by the Lewis acid sites. 29Si, 27A1 and 23Na NMR measurements were quite useful to identify the solid reaction products.
30-P-20 - Zeolite-containing photocatalysts for treatment of waste-water from petroleum refineries A.K. Aboul-Gheit and S.M. Ahmed
Egyptian Petroleum Research Institute, Nasr City P.O. Box 9540, Cairo 11787, Egypt. E Mail [email protected] Photocatalytic degradation of petroleum representative hydrocarbons (o-xylene > decaline > n-hexadecane) was investigated using metal-phthalocyanines (Pcs) combined with Na-zeolites (1:1) as photocatalysts. This combination was found significantly synergistic, n-Hexane photodegradation was examined using : a) CuPc mixed with Na-mordenite, Na-Y, Na-Beta or Na-ZSM-5, b) CuPc mixed with Na-, H- and dealuminated-mordenite, and c) Pcs having different central oxidative metals: Ce, Co, Mn, Fe, Cr or Cu, mixed with Na-Beta zeolite. Crude oil photodegradation was also examined using the catalysts of item c). The illumination period for pure hydrocarbons testing was 15 minutes, whereas for crude oil was one week. Kinetics using Langmuir-Hinshelwood models was successful.
325
30-P-21 - Autoreduction of Cu 2+ species in Cu-ZSM-5 catalysts studied by diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry and elemental analysis G. Moretti a, G. Ferraris a and P. Galli b
a Centro CNR "SACSO", bDipartimento di Chimica, Universitdt "La Sapienza", [email protected], Roma- Italy The autoreduction process of Cu 2+ species in Cu-ZSM-5 catalysts, with Si/A1 = 80 and copper exchange levels 81 and 536 %, was studied by means of spectroscopic (in-situ diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy) and chemical methods (thermogravimetry in N2, elemental analysis, adsorption-desorption of N2 at 77 K and adsorption of N2 at 273 K). It appears that on the fresh catalysts (treated in air at 383 K) the majority of Cu 2+ species may be reduced to Cu +, under vacuum or in a flow of inert gas at high temperature, by means of the carbonaceous deposits left in the ZSM-5 matrix due to the incomplete burning of the organic template used in the zeolite synthesis.
30-P-22 - Performance of bi-and tri-metallic mordenite catalysts for the lean SCR of NOx by methane F. Bustamante (a), P. Avila (b) and C. Montes de Correa (a)
a Dept. of Chemical Engineering, Universidad de Antioquia, [email protected] b Instituto de Catdlisis y Petroleoquimica, CSIC 28049 Madrid. Espagta The lean NOx reduction by CH4 in the presence of 10-15% water vapor was studied on biand tri-metallic powder catalysts containing two or three of the following species: Co, Pd, Ce, and Pt on HMOR. A cooperative effect in the Pd-Co, Pd-Ce, Pd-Ce-Co and Pd-Pt-Ce systems was found for CH4-SCR under wet conditions. Pd-Ce/HMOR and Pd-Ce/Co-HMOR catalysts were more tolerant to the coexistence of H20 and SO2 in the gas feed than Pd/Co-HMOR. Co, Pd and Ce species were impregnated on ceramic monoliths washcoated with mordenite. The results of NOx reduction were different for the monolithic and powdered catalysts. However, a similar trend in the CH4-SCR activity of both catalyst types was observed.
30-P-23 - Total oxidation of volatile organic compounds - catalytic oxidation of toluene over CuY zeolites A.P. Antunes (a), J.M. Silva (b), M.F. Ribeiro (a), F.R. Ribeiro (a), P. Magnoux (c) and M. Guisnet (c)
a lnstituto Superior T~cnico, DEQ, Lisboa, Portugal, e-mail.'[email protected] b Instituto Superior Engenharia de Lisboa, DEQ, Lisboa, Portugal c Universit6 de Poitiers, UMR 6503, 40 Av. Recteur Pineau, 86022 Poitiers, France Transformation of toluene in low concentration (800 ppm) in air over CuY zeolites containing different copper contents and Si/A1 ratios was studied at temperatures between 150 and 500~ It was found that total oxidation is promoted on non dealuminated catalysts and depends on the copper content. The most active catalysts correspond to the catalysts with Cu contents that are close to the complete exchange of the zeolite. The presence of sodium cocations in CuY zeolites increases their combustion efficiency, by improving the dispersion of ionic copper species and preventing the formation of CuO clusters.
326
30-P-24 - Study on relationship between the local structures of Ti-HMS mesoporous molecular sieves and their photocatalytic reactivity for the decomposition of NO into N2 and 02 J. Zhang, a B. He, a M. Matsuoka, b H. Yamashita b and M. Anpob
a Institute of Fine Chemicals, East China University of Science and Technology, 7, China," [email protected]; b Dept. of Applied Chemistry, Graduate School of Engineering Osaka Prefecture University, 1-1, Gakuen-cho, Saka, Japan Titanium oxide species included within the framework of mesoporous zeolites (Ti-HMS) were studied using nitrogen adsorption/desorption. These mesoporous materials exhibited high and unique photocatalytic reactivity for the direct decomposition of NO into N2, N20 and 02 at 275K.
30-P-25 - Influence of synergistic effects on the selective catalytic reduction of NOx with CnHm over zeolites S.N. Orlik and V.L. Struzhko
L. V. Pisarzhevsky Institute of Physical Chemistry of NAS of Ukraine 03039, Pr.Nauki, 31, Kiev, Ukraine, fax: (044) 265 62 16; e-mail: [email protected] A synergistic effect leading to the increased catalyst activity and selectivity in selective catalytic reduction (SCR) of NO with methane or propane-butane mixtures was found when cobalt, calcium and lanthanum cations were introduced into the protic MFI-type zeolite. This non-additive increase of the zeolite activity is attributed to increased concentration of the BrOnsted acid sites and their defined location as result of interaction between those and cations (Co, Ca, La). Activation of the hydrocarbon reductant occurs at these centers. Doping the H-forms of zeolites (pentasils and mordenites) with alkaline earth metal and Mg cations considerably increased the activity of these catalysts and their stability to sulfur oxides.
30-P-26 - Catalytic properties of Fe-Co double synthesised with beta zeolite for toluene oxidation
layered
hydroxides
J. Carpentier, S. Siffert, J.F. Lamonier and A. Abouka'/s
Laboratoire de Catalyse et Environnement, E.A. 2598, Universit~ du Littoral- C6te d'Opale, MREID, 145, avenue M. Schumann, 59140 Dunkerque, France, [email protected]. Fe-Co layered double hydroxides with Co/Fe ratios of 2 and 3 were prepared with or without the presence of Beta zeolite and their catalytic potential was tested in toluene total oxidation. These calcined solids synthesised with [3-zeolite were less active and selective than those prepared without zeolite. However, a mechanical mixture of 1/3 Fe,Co-LDH (Co/Fe - 3) + 2/3 Na[3-zeolite presented higher catalytic performance which could be explain by a synergetic effect of the both Fe,Co-double oxide and [3-zeolite. The mechanism could undergo through a spillover of the adsorbed toluene from zeolite, which has a high toluene storage/release capacity, to the Fe,Co double Oxide, which is highly performant for this oxidation.
327
30-P-27 - Selective catalytic reduction of NO over Fe z e o l i t e s - catalytic and i n - s i t u - D R I F T S studies F. Heinrich, E. L6ffler and W. Grtinert Lehrstuhl Technische Chemie, Ruhr-UniversitOt Bochum, P. O. Box 102148, D-44 780 Bochum, Germany An in-situ DRIFTS study of a Fe-ZSM-5 catalyst during the selective catalytic reduction of NO by isobutane is reported. The catalyst was prepared by vapour-phase exchange of HZSM-5 with FeC13. Catalytic data from in a micro-catalytic flow reactor have been in principle reproduced by using the DRIFTS cell as a flow reactor. Adsorbates, transient intermediates, and interactions of zeolite OH groups have been monitored at 873-523 K, with concomitant NO conversion measurement. It has been found that the spectra of deposits formed on H-ZSM-5 and Fe-ZSM-5 are identical at 523 K. In formation about the deposits obtained at 523 K was not representative for the temperature of peak NO conversion
3 0 - P - 2 8 - Selective catalytic reduction of NO by methane over A g N a Z S M - 5 catalysts in the excess of oxygen C. Shi a,b, M. Cheng a, Z. Qu a, X. Yangb and X. Bao a* a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, The Chinese Academy Sciences, Dalian 116023, P. R. China, [email protected] b Laboratory of Plasma Physical Chemistry, Dalian University of Technology, Dalian 116024, P. R. China AgNaZSM-5 catalysts were investigated for the selectively catalytic reduction of NO by methane in the excess of oxygen. It was clearly depicted that the conversion rate of NO to N2 had a linear dependence on the silver loading (4.32-~13.64%), which indicated that all silver species in the zeolite were active for the CH4-SCR reaction. The presence of excessive oxygen in the feed gas favored the CH4-SCR reaction. The temperature programmed desorption profiles in He and 2%CH4/He after the co-adsorption of NO and 02 revealed that surface nitrates were formed on silver catalyst, and could be effectively reduced by methane
30-P-29 - Z S M - 5 / R a n e y Fe composite used as D e N O x catalyst B. Zong, W. Wang, L. Lu and X.T. Shu Research Institute of Petroleum Processing, China Petrochemical Cooperation, Beijing, China Zeolite ZSM-5 was grown onto Raney Fe powder and wire gauze. ZSM-5/Raney Fe was used as catalyst for the selective reduction of NO with NH3 in the presence of 02, SO2 and H20. DeNOx activity of the composite catalysts were found to be increased after hydrothermal treatment. Migration of Fe from Raney Fe into zeolite ZSM-5 during the treatment contributes to the high performance of the ZSM-5/Raney Fe of DeNOx reaction. Using the technique of growth the zeolite in situ on Raney Fe, high hydrothermal stability and high mechanically strength catalytic packing of any required shape can be produced. The composite ZSM5/Raney Fe is promising catalyst for industrial DeNOx processing.
328
30-P-30 - Reduction of nitric oxide by hydrocarbons on Ni-ion exchanged zeolites B.I. Mosqueda-Jim6nez a'b, M. Brandmair a, A. Jentys a, K. Seshan b and J.A. Lercher a
a Technische Universit~it Mfinchen, Garching, [email protected], Germany b Faculty of Chemical Technology, University ofTwente, Enschede, The Netherlands The reduction of NO in the presence of excess oxygen with propane and propene over Niexchanged zeolites was studied. Incorporation of Ni led to the formation of Bronsted acid sites resulting from the hydrolysis of divalent Ni ions. Calcined catalysts showed a high selectivity to N2 formation, while after reduction of the Ni species significant concentrations of NO2 and N20 were formed. Higher NO conversions were obtained with propane compared to propene except for NiNaMOR catalysts with low nickel content. The concentration of acid sites did not play a major role in the NO reduction, high acid site concentrations, however, resulted in the formation of coke.
30-P-31- NOx Reactivity on microporous catalytic studies
MeAPOs. spectroscopic
and
A. Frache a, M. Cadoni a, S. Coluccia b, L. Marchese a*, B. Palella c, R. Pirone ~ and P. Ciambelli e
aDitz~'mento a~Scienzee tecr~logieAvamate, Universitgtdel Piemonte On'entaleA l e s s ~ Italy. ~chese(~;h wTito.it,"bDipartimentodi Chimica IFM, Universitgtdi Torino CDi~mento di l n g e ~ Chimic~ (fniversithdi Ntg~oli "FedericolI", N#~ol~ Italy. dlstitutook"Ricerchesulla Combus#one, CNR, Ncg~oli, Italy,"e o l ~ F l t O ~"I n g e ~ Chimicae Alimentare, Untversitgtdi Salerno, Italy. NOx reactivity on microporous aluminophosphates and silico-aluminophosphates containing Co and Cu ions in A1PO4-34, -5 and -11 type structures, is reported. CoAPO-34 is very efficient catalyst in the NO oxidation to NOz reaching the equilibrium conversion value at 350~ wfiereas is inactive in the NO reduction by CO, a reaction which, on the contrary, p ~ efficiently on Cu-based catalysts (specially in the 300-550~ range). N20 decomposition and NO oxidation to NO2 are also effective on Cu-containing catalysts, and followed the sequence of activity: Cu-SAPO-34 _>CuAPSO-34 > CuAPO-34 > CttAPO-5 ~ ChaAPO-11. NO adsorption on the most active catalysts was investigated by FTIR and this showed that Cu2+ and Cu+ mononitrosyl complexes were formed in much larger amount on the silicon-containingcatalysts.
30-P-32 - Adsorption characteristics on zeolite catalysts for hydrocarbon removal under cold-start engine condition H.K. Seo, J.W. Oh and S.J. Choung
School of Environmental and Applied Chemistry, KyungHee University, 449-701 Suwon, Korea, [email protected] Air pollution, mainly contributed by the emission from automobiles, has become the most serious urban environmental problems in many countries. In this study, so as to meet the SULEV regulation, the main idea has been focused on the utilization of HCA(Hydro-Carbon Adsorber) in order to adsorb the excess hydrocarbons emitted during the period of engine cold-start. As a main recipe of HCA materials, many types of zeolite as well as the combination of alumina, precious metals were used. In this study, physico-chemical factors of zeolite such as acidic properties and hydrophobic properties etc. has been characterized, and tried to find the optimum recipe of HCA materials. As results, among the acid properties of zeolites, the Si/A1 ratio is found to be the most important factor to get higher hydro-carbon adsorption capacity.
329
3 0 - P - 3 3 - In-situ synthesized Z S M - 5 on decomposition on the monolithic catalysts
cordierite
substrate
and
NO
N. Guan *a, X. Shan a, X. Zeng a, S. Liu a, S. Xiang a, U. Illgen b and M. Baerns b
aDepartment of Chemistry, Nankai University, Tianjin P.R. China; blnstitute of Applied Chemistry, Rudower Chaussee 5, Berlin-Adlershof Berlin, Germany For obtaining a monolithic catalyst with better mechanical and hydrothermal durability, ZSM5 zeolite with different Si/A1 ratios (60, 55, 40, 25, 15) have been synthesized in-situ on cordierite honeycomb substrate. SEM photos showed the different crystal size from sample to sample. Solid MAS NMR was used to determine Si/A1 ratios and the amount of zeolite on the substrate by the peak intensity 29Si. Investigation of NO decomposition (2000 ppm NO in He) on the Cu-exchanged ZSM-5/cordierite monolithic catalysts was performed at 723 K, GHSV=I 0,000/h. Results proved that the TOF of NO decomposition on monolithic catalysts is comparable with pure zeolite catalysts.
30-P-34 - Selective reduction of N O to N2 in the presence of oxygen T. Furusawa (a), K. Seshan (b), S.E. Maisuls (b), J.A. Lercher (c), L. Lefferts (b) and K. Aika (a)
alnterdisciplinary Graduate School of Science & Technology, Tokyo Institute of Technology, Japan [email protected].]p; bFaculty of Chemical Technology, University of Twente, The Netherlands," Clnstitutfiir Technische Chemic, Technische Universitgtt Mfmchen, Garching Germany Catalytic performance of Co-ZSM5 (Si/AI=I 1) prepared by SSIE (Solid State Ion Exchange) method was compared with that of Ag-ZSM5 prepared by LSIE method for the selective reduction of NO with propylene in the presence of oxygen. It was found that C3H6 acted as a reductant more effectively for production of N2 over Ag-ZSM5 than Co-ZSM5 and that a route for producing N2 exclusively existed over Ag-ZSM5 from the kinetic results.
30-P-35 - Catalytic behaviour of Co-exchanged ferrierite for lean N O x - S C R with methane D. Sannino, M. Concetta Gaudino and P. Ciambelli
Dipartimento di Ingegneria Chimica e Alimentare, Universith di Salerno, 84084 Fisciano (SA), Italy. sannino@dica, unisa, it Lean NOx-SCR with CH4 has been investigated on Co-modified synthetic ferrierite prepared in different conditions of ion exchange (temperature, time, precursor zeolite composition). A maximum NOx conversion (50% at 100% CH4 conversion) was obtained at 500~ Activity and selectivity depend on the nature of Co species (from mononuclear to polynuclear cationic to oxidised phases) formed into ferrierite. The effect of side reactions such as uncatalysed and catalysed methane combustion on catalytic performance is discussed.
330 03- New Methods of Zeolite Synthesis (Thursday) 0 3 - P - 0 6 - Zeolitization of a spanish bentonite in seawater medium. Effect of
alkaline concentration and time R. Ruiz, C. Blanco, C. Pesquera and F. Gonzzilez
Dept. de Quimica. Univ Cantabria, [email protected], Santander (Spain). In this study a bentonite was modified to a zeolitic material by alkaline treatment in a seawater medium. The structural and textural characteristics of the clays modified in this medium were determined and compared with those of the natural clay and with those of the clays m.odified under the same conditions but in distilled water. The samples were characterized by XRD, IR, TG and SEM. The modifications observed in the composition of the resulting zeolitic products depend not only on the NaOH concentration and treatment time but also on the nature of the synthesis media. The zeolitic products synthesized in seawater showed higher crystallinity and less heterogeneity. The treatment can be designed according to the characteristics required for the process in which the zeolitic product will be applied. 03-P-07-
Silicalite-I spheres prepared from preformed resin-silicate
composites L. Tosheva and J. Sterte
Division of Chemical Technology, Luledt University of Technology, Luledt, Sweden, [email protected] Silicalite-1 spheres were prepared in two steps by treating resin-silicate composite particles with structure-directing template solutions. In a first step resin-silicate composites were obtained as a result of an ion exchange of silica species within macroporous anion exchange resin beads. In a second step the composite particles were hydrothermally treated in structuredirecting template solutions at 170~ for 24 h. Finally, the organic components were removed by combustion at 600~ A number of samples were prepared using TPAOH and TPABr solutions of different concentrations as well as different weight ratios between template solution and composites. 03-P-08 - The synthesis of offretite single crystals using pyrocatechoi as
complex agent F. Gao (a), G. Zhu (a, b), Xiaotian Li (a), S. Qiu (a*), B. Wei (a), C. Shao (a) and O. Terasaki(b)
a Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Department of Chemistry., Jilin University, Changchun, P. R. China, e-mail: [email protected] b CREST, Department of Physics, Tohoku University, Sendai, Japan. Offretite single crystals with perfect morphology have been succesfully synthesized using pyrocatechol as complex agent. Compared with other methods, zeolite offretite prepared in this system has much larger size and better morphology. The influence of pyrocatechol has been studied, and the XRD patterns and the SEM photographs of offretite single crystals have been shown. The role of pyrocatechol has been characterized by 27 A1 NMR and 29 Si NMR, which show that an aluminum-pyrocatechol complex is formed in the reaction gel.
331 03-P-09 - Synthesis of FER type zeolite in presence of tetrahydrofuran G.-Q. Guo (a, b), Y.-J. Sun (c) and Y.-C. Long (a*) a Department of Chemistry, Fudan University, Shanghai 200433, P. R. China, b Research Institute ofBeijng Yanshan Petrochemical Corporation, SINOPEC, Beijing 102500, P. R. China, [email protected] c Center of Analysis and Measurement, Fudan University, Shanghai 200433, P. R. China FER zeolite can be prepared by spontaneous crystallization under hydrothermal conditions from the reactant with molar composition of 0.5 THF (tetrahydrofuran)-o0.215NazO eSiOze0.05AlzO3e20H20. The influence of SIO2/A1203 molar ratio, alkalinity, amount of template and reaction temperature was explored as well.
03-P-10 - Utilization of dry-gel conversion method for the synthesis of gailosilicate zeolites beta, ZSM-5 and ZSM-12 R. Bandyopadhyay (a), Y. Kubota (a), S. Nakata (b) and Y. Sugi (a)* a Department of Chemistry, Faculty of Engineering, Gifu University, Gifu-501-1193, Japan Email" [email protected]; Fax. 81-58-293-2597 b Department of Materials-process Engineering and Applied Chemistry for Environment, Faculty of Engineering and Resource Science, Akita University, Akita O10-8502, Japan Synthesis of gallosilicate zeolites [Ga]-beta, [Ga]-ZSM-5 and [Ga]-ZSM-12 was performed by dry-gel conversion (DGC) method. The crystallization of the dry gel was performed in presence of small amount of water, without which the crystallization failed. The method was convenient and as effective as conventional hydrothermal method. The samples were pure and highly crystalline, and showed characteristic of typical gallosilicate zeolites.
03-P-I 1 - A novel method for the synthesis of cancrinite type zeolites C.F. Linares (a), S. Madriz (b), M.R. Goldwasser (b) and C. Urbina de Navarro (c) a Universidad de Carabobo. Dpto de Quimica, clinares@thor, uc. edu. re, Venezuela. b Universidad Central de Venezuela, Caracas, Venezuela c Centro de Microscopia Electr6nica, UCV, Caracas, Venezuela A novel method for the synthesis of cancrinite type zeolites was developed by modification of an X faujasite type zeolite. Synthesis parameters such as crystallization time (16 h), temperature (80~ and pressure (autogenous pressure) were highly reduced by this procedure compared to previous synthesis methods. A 100% conversion of the ZX to cancrinite was observed with crystallinity higher than 80%. No other phases different to that of the cancrinite were observed. The basic character of the cancrinite was ascertained by means of its catalytic activity in the Knoevenagel condensation reaction.
332
03-P-12 - High-throughput strategies for the hydrothermal synthesis of zeolites and related materials N. Stock (a), N. Hilbrandt (a), K. Choi (b) and T. Bein (a)
a Department Chemie, Ludwig-Maximilians-Universitgit Manchen, Butenandtstr. 5-13, 81377 Mfinchen, Germany b Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA We have developed an automated parallel synthesis methodology that permits the rapid and detailed investigation of hydrothermal systems. The general procedure is as follows: automatic dispensing of reagents into autoclave blocks followed by synthesis, product isolation and automated structure analysis with X-ray diffractometry. Here we describe the application of this technique to the exploration of the aluminophosphate synthesis field. The effects of template, template concentration, A1 sources as well as mixed template systems are investigated. Emphasis is put on the study of cooperative structure direction effects.
03-P-13 - Static zeolite MCM-22 synthesis using two-level factorial design J. Warzywoda, S. Dumrul, S. Bazzana and A. Sacco, Jr.
Centerfor Advanced Microgravity Materials Processing, Chemical Engineering Department, Northeastern University, Boston, MA 02115, USA, [email protected]. A 2 4 factorial experiment (factors: the SIO2/A1203 (A), H2SO4/Na20 (B), and Hexamethyleneimine (HMI)/SiO2 (C) ratios of the synthesis mixture, and the synthesis time (D)) was carried out to study the crystallization behavior of MCM-22 grown statically without aging in a broad reaction composition range. The four-factor interaction was significant (i.e., none of the factors acted independently) in influencing the crystallization kinetics of MCM22. The two three-factor (A.B.C and A.B.D) interactions were significant (i.e., none of the factors acted independently) in influencing the average MCM-22 particle size. The feasibility of using the lower amounts of HMI, and more siliceous synthesis mixtures than before to statically grow highly crystalline MCM-22 was demonstrated.
03-P-14 - Influence of nano-particle properties of MFI zeolite
agglomeration
on the catalytic
S. Inagaki, I. Matsunaga, E. Kikuchi and M. Matsukata*
Department of Applied Chemistry, Waseda University,3-4-10kubo, Shinjuku, Tokyo, 1698555, Japan, *[email protected] Microstructures of spherical and coffin-shaped MFI zeolite and its influence on catalytic activity for cumene cracking were investigated. While spherical MFI was composed of nanoparticles, coffin-shaped one possessed a layered structure where "nano-particles" with ca. 30 nm in size were accumulated on the dense core. Both the thickness of nano-particles layer and mesopore volume linearly correlated with the activity for cumene cracking, suggesting that the mesopores in MFI particles formed during "nano-particles" agglomeration, and that the reaction rate of cumene cracking was significantly influenced by the diffusion of cumene molecule in the nano-particles agglomerating layer.
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0 3 - P - 1 5 - Rapid and mass production of porous materials using a continuous microwave equipment D.S. Kim, J.M. Kim, J.-S. Chang and S.-E. Park*
Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology (KRICT), Yusung, Taejon 305-600, Korea," [email protected] A continuous microwave equipment (CME) has been developed to achieve a rapid and mass production for ZSM-5 and NaY zeolite. A precursor mixture for synthesis of ZSM-5 was prepared by mixing aluminosilicate gel with a nanoseed solution obtained under microwave irradiation, and pumped into the CME. Duration time in the CME was 5 min to accomplish the crystallization of ZSM-5 under microwave irradiation. For NaY zeolite, the precursor gel without nanoseeds was introduced into the CME and crystallization time was within 30 min. XRD and SEM results indicate that the structural properties of ZSM-5 and NaY zeolite obtained are similar to those obtained using batch-type microwave instrument and by conventional hydrothermal synthesis.
0 3 - P - 1 6 - Hydrothermal synthesis of vanadium-containing microporous aluminophosphates via the design of experiments approach L. Frunza (a,b), P. Van Der Voort (c), E.F. Vansant (c), R.A. Schoonheydt (b) and B.M. Weckhuysen (b)
a National Institute of Materials Physics, Bucharest, [email protected], Romania b Centrum voor Oppervlaktechemie en Katalyse, K. U Leuven, Belgium c Department Scheikunde, U.I. Antwerpen, Belgium An experimental design has been applied to the hydrothermal synthesis of VAPO-11 molecular sieve (AEL structure) from a VOSO,.5H20"AI(iPrO)3"Pr2NH'H,O gel. Statistical models that relate the selected synthesis variables with the crystallinity are proposed. The optimal synthesis conditions for the two structures (single phase or physical mixture with the AFO (VAPO-41) structure) are inferred from the models and compared with the literature data on single phase synthesis. Highly crystalline single-phase VAPO-11 can be best prepared at 170~ from a synthesis gel with low vanadium content and high water content.
03-P-17 - Synthesis of a thin Silicalite-1 membrane, through sintering, for use in a membrane reactor E.E. McLearya, A.W. Hoogestegera, R.D. Sanderson a and J.C. Jansen a'b
alnstitute of Polymer Science, Faculty of Natural Science, Stellenbosch University, South Africa," bLaboratory of Applied Organic Chemistry and Catalysis, Delft University of Technology, Delft, The Netherlands To meet the dual challenge of selectivity and permeability for membranes used in reactors, there has been a thrust to support thin layers of highly selective membrane material on a porous support with high permeability. In this report we present the synthesis of such a thin molecular sieve layer of Silicalite-1 on a c~-A1203 support through the sintering of colloidal zeolite crystals (---150 nm) deposited with the Langmuir-Blodgett technique on the support.
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03-P-18 - Mixed alkali templating in the Si/A! = 3 and 10 systems" a combinatorial study G.J. Lewis a, D.E. Akporiaye b, D. Bem a, C. Bratu a, I.M. Dahl b, A. Karlsson b, R.C. Murray a, R.L. Patton a, M. Plassen b and R. Wendelbo b aUOP LLC, g/[email protected], Des Plaines, IL USA ; bSINTEF, Blindern, Oslo, Norway A combinatorial approach is used to investigate mixed alkali templating in the Si/A1 = 3 and 10 zeolitic systems. The experimental design includes 15 high-symmetry alkali combinations of Li +, Na +, K + and Cs +, decoupled variations in total hydroxide and total alkali, and four digestion conditions giving 960 reactions. Compositional fields for BEA, ANA, MER, LTL and pollucite (ANA-Cs), interactions between alkali cations in the templating process, and the use of Principle Components Analysis to streamline the analysis of large XRD data sets are presented.
03-P-19 -Factors affecting composition and morphology of mordenite F. Hamidil, M. Pamba 2, A. Bengueddach 3, F. Di Renzo4 and F. Fajula 4 ID6partement de Chimie, USTO, B.P. 1505 Elmenaouar, Oran, Algeria 2Lab. Physique de la Matibre Condens~e, Universit6 Montpellier 2, Montpellier, France 3Lab. Chimie des Mat6riaux, Universit6 0ran Es-Senia, Oran 4Lab. Mat6riaux Catalytiques et Catalyse en Chimie Organique, ENSCM, Montpellier The shape and size of the crystals of mordenite, as well the Si/AI ratio, have implications on industrial applications in hydrocarbon conversion and separation. The ratio between the incorporation yields of silicon and aluminium is inversely proportional to the alkalinity level. Increased solubility of silica at higher pH accounts for the decrease of incorporation of silicon. The source of silica and the ageing of the synthesis gel also influence the final Si/AI ratio. The alkalinity of the synthesis system is also the main factor affecting the morphology of the mordenite crystals, flatter crystals being formed at low alkalinity.
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0 4 - Isomorphous substitutions (Thursday) 0 4 - P - 0 6 - Uniform distribution of nickel during the synthesis of Si-ZSM-5 through solid-state transformation M. Salou, Y. Kiyozumi, F. Mizukami,* S. Niwa, M. Imamura and M. Haneda
National Institute of Materials and Chemical Research, [email protected], Japan Ni-containing Si-ZSM-5 was prepared through solid-state transformation, from kanemite and from TEOS, by adding nickel nitrate directly to the synthesis mixture. For both silica sources, nickel was found to be present at the outer surface and in the main channels of the zeolite. The outer surface nickel could be highly dispersed for a given Ni/Si ratio. In the case of TEOS, most of the nickel was present at the surface whereas in the case of kanemite, the distribution of nickel was more balanced between the surface and the bulk. The comparison with impregnation showed that the interaction of nickel with the zeolite framework was increasing in the order impregnation << direct synthesis-TEOS < direct synthesis-kanemite. 0 4 - P - 0 7 - Synthesis, characterization and catalytic activity of FeBEA and FeMFI zeolite obtained by xerogel wetness impregnation O.A. Anunziata (a), L.B. Pierella (a), E.J. Lede (b) and F.G. Requejo (b,c)
aCentro de Investigaci6n y Tecnologia Quimica(CITeQ) UTN-FC- Cordoba-Argentina bDto. Fisica, Fac. Cs Ex, UNLP and IFILP (CONICET), La Plata, Argentina ~Present address." Material.Science Division., LBNL, Berkeley, CA, USA Fe-containing zeolites with MFI and BEA type structure were prepared by a novel method using amorphous SiO2/Fe203 xerogel. The dependence of the synthesis conditions on crystallinity, structure and catalytic activity and its characterisation by BET, FT-IR, XRD, EXAFS, XANES and TPD were investigated. XANES spectra are sensitive to the chemical state of the element and depend on the oxidation state, the binding mode, and the ligand atoms. The results obtained with the characterization methods confirmed that the Fe-zeolites synthesis by new xerogel method gave Fe in framework position with tetrahedral symmetry.
04-P-08 - A novel method for the synthesis of chromium aluminosilicate with BEA structure X.-H. Tang, L.-R. Pan, J.-Z. Wang and H.-X. Li
Department of Material Science, College of Chemistry, Nankai University, Tianjin 300071, [email protected], P. R. China A novel method has been developed for hydrothermal synthesis of zeolite beta with high chromium content and low aluminum content under static conditions. The crystalline phase and spectroscopic property of this material were characterized by means of XRD, XRF, IR, UV-Vis DRS, ESR and SEM. The results revealed that part of the chromium ions were incorporated into the zeolite framework during crystallization. Using tris(acetylacetonato) chromium(III), [Cr(C5H702)3], as a chromium source, Cr/Si molar ratio can be up to 1/48 in the calcined and ion-exchanged sample. The chromium aluminosilicate exhibited a high oxidative activity in the presence of dilute H202.
336
04-P-09 - Pure SAPO, CoAPSO and ZnAPSO ATO-like molecular sieves through optimized synthesis procedures A. Azzouz (a), N. Bilba (b), M. Attou (c), A. Zvolinschi (a) and S. Asaftei (a) a Engineering Faculty, Bacau University, Romania, [email protected] b Faculty of Chemistry, The "AI.I. Cuza" University, Iasi, Romania c Laboratoire de Synthese Organique, CDM, Draria, Algeria Pure SAPO-31, CoAPSO-31 and ZnAPSO-31 were hydrothermally synthetized in the presence of dipropylamine, using a 33 factorial experiment, in the temperature range 200210~ for 24-27 hours, from mixtures of molar composition: 1.2 A1203: 1.03P205: xSiO2:1.7 (n C3H7)zNH :IHF: 62H20 and A1203 : 1.03P205 : xSiO2 : y(Metal)205 : 1.7(n C3H7)zNH: 1HF: 62H20. Strong interactions were observed between the parameter effects but no synergy phenomena occur. SAPO-31 can be obtained within relatively wide parameter ranges. Pure CoAPSO-31 and ZnAPSO-31 can be synthesized using small Si content in the starting gels.
04-P-10- Relation between amount of the niobium ammonium complex in the reaction mixture and the crystal size of a Nb- MFI zeolite A.H. Munhoz jr.a; S. Rodriguesb; P.K. Kiyohara c and W. Sano c aDepto.Eng. Materials-U.P.Mackenzie & Depto Eng. Quimica-UNIBAN- Brazilahmunhoz@yahoo, corn bDepto.Eng. Quimica - U.S.P. - rodrigus@usp, br CInstituto de Fisica - U.S.P. - sano@ifusp, br A zeolite with MFI structure was synthesised with 3 different amounts of niobium ammonium complex (NAC) in the reaction mixture. The samples obtained were characterised by scanning electron microscopy (SEM) using secondary electron detector and energy dispersive spectrum (EDS) detector, X-ray diffraction (XRD), differential thermal analysis (DTA), and electron paramagnetic resonance (EPR). The increase of NAC in the reaction mixture results in the decrease of the crystal size of the zeolite. The characterisation shows evidence that the niobium was incorporated into MFI structure.
04-P-II - Spectroscopy of the formation of microporous transition-metal ion containing aluminophosphates under hydrothermal conditions B.M. Weckhuysen (a,b), D. Baetens (a) and R.A. Schoonheydt (a) a Centrum voor Oppervlaktechemie en Katalyse, Departement Interfasechemie, K.U.Leuven, Kardinaal Mercierlaan 92, 3001 Heverlee, Belgium. E-mail." Bert. Weckhuvsen~agr.kuleuven.ac.be b Departement Anorganische Chemie en Katalyse, Debye lnstituut, Universiteit Utrecht, P.O. Box 80083, 3508 TB Utrecht, The Netherlands
In-situ DRS spectroscopy has been used to investigate the crystallization process of MeAPO5 molecular sieves (with Me = Co, Cr, Ni and V) as a function of the synthesis time and conditions. A specially developed synthesis cell was used, which allows to probe the coordination environment of the transition metal ions in-situ during hydrothermal conditions and to obtain high-quality molecular sieves starting from a homogeneous synthesis gel.
337
04-P-12 - Co-templated synthesis of C r A P O - 5 with various organic acids J. Kornatowski (a), G. Zadrozna (a), J.A. Lercher (a) and M. Rozwadowski (b) a Technische Universitdit Manchen, TC 11,[email protected], Germany b Nicholas Copernicus University, Faculty of Chemistry, Torun, Poland Most of the 20 tested saturated, unsaturated, and bifunctional aliphatic acids can be used as co-templates for CrAPO-5. The acid type and amount affect significantly the crystallinity, the content of substituted Cr, as well as the dimensions and morphology of the crystals. The cotemplating role of the acids is clearly visible, however, a systematic correlation with the resulting crystal properties is not observed. The acid has to be chosen with respect to the required product properties. The highest crystallinity is observed with acetic, acrylic, methacrylic or crotonic acids, the most perfect morphology is obtained with unsaturated acids of C3 to C6 chain length and the highest substitution of Cr with C3 to C5 bifunctional acids. Only methacrylic acid seems to satisfy all the above requirements to a relatively high extent.
04-P-13 - H o w to increase the a m o u n t of f r a m e w o r k Co 2+ in m i c r o p o r o u s crystalline a l u m i n o p h o s p h a t e s ? W. Fan a', R.A. Schoonheydt a and B.M. Weckhuysen a'b aCentrum voor Oppervlaktechemie en Katalyse, Departement lnterfasechemie, K. U. Leuven, E-mail." Bert. Weckhuysen@agr. kuleuven, ac. be bDepartement Anorganische Chemie en Katalyse, Debye lnstituut, Universiteit Utrech Using the synthesis of CoAPO-5 and CoAPO-CHA molecular sieves as examples, the influence of the synthesis conditions the solvents as well as the presence of monovalent countercations and structure-directing organic template molecules on the isomorphous substitution degree of Co for A1 in microporous crystalline aluminophosphates are studied. It was possible to prepare CoAPO-5 with more than 25% of the framework A1 sites substituted by Co 2+, CoAPO-CHA with Co 2+ occupying most of the framework AI sites ([Co]:[A1]>I) and a new cobalt phosphate material.
04-P-14 - Preparation of zinc containing zeolite catalysts A. Katovic(a), E. Szymkowiak (b), G. Giordano (a), S. Kowalak (b), A. Fonseca (c) and J. B.Nagy (c) (a) Dipartimento di ]ngegneria Chimica e dei Materiali, Universit?~ della Calabria, via P. Bucci, 1-87030 RENDE (CS), Italy (b)Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznan, Poland (c) Laboratoire de RMN, Facult6s Universitaires Notre-Dame de la Paix rue de Bruxelles 61, B-5000 NAMUR, Belgium A method is described for the preparation of zinc-containing zeolite by direct synthesis from hydrogels. The synthesis of Zn-MFI type zeolite materials and the post synthesis introduction of Cu are discussed. The samples are characterized by XRD, AAS, thermal analysis, SEM and 29Si-NMR spectroscopy. The catalytic results on the cumene conversion are discussed.
338
04-P-15 - Synthesis of Zn and Fe substituted mordenite using citric acid as eomplexing agent M. Dong, J.-G. Wang* and Y.-H. Sun State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001, Shanxi, P. R. China Email." iccjgw@sxicc, ac. cn A complexing agent, citric acid, is employed in the synthesis of zincosilicate and ferrisilicate mordenites. Evidences for the incorporation of heteroatoms in the lattice framework have been obtained from ICP, CRD, FTIR, and SEM. The presence of citric acid enhances the ratios of crystallization for the Zn- and Fe-substituted mordenites, promotes the crystallinity of the products, and increases the heteroatomic contents in the lattice framework as well. It is speculated that the citric acid may decrease the concentration of metal ions in the synthesis gel, thereby prevent the unfavorable formation of oxide or hydroxide species.
04-P-16 - ET(Zr)S-4 molecular sieve: kinetic and morphological characterization D. Vuono a, P. De Luca a, A. Fonsecab, J. B.Nagyb and A. Nastro a
a) Department of Pianificazione Territoriale, University of Calabria, Arcavacata di Rende, 87030 Rende (Cs), Italy. b) Laboratoire de R.M.N., Facult6s Universitaires Notre-Dame de la Paix, B-5000 Namur, Belgium. The purpose of this research is to study the crystallisation kinetics of ET(Zr)S-4 starting from mixed systems containing titanium and zirconium and to connect the results obtained to the observation, through electron microscopy (SEM), of the crystal morphology of ETS(Zr)-4 synthesised at different reaction times. The 29Si NMR data suggest that zirconium occupies framework tetrahedral positions.
0 4 - P - 1 7 - Influence of alcali cations on the incorporation of iron into MFI structure in fluoride media F. Testa a, F. Crea a, R. Aiello a, K. Lfizfirb, P. Fejes c, P. Lentz d and J. B.Nagyd
~Dip. di Ingegneria Chimica e dei Materiali, Univ. della Calabria, 1-87030 Rende (CS) Italy bInstitute of Isotope and Surface Chemistry, 1525 Budapest, P.O. Box 77, Hungary ~University of Szeged, Applied Chemistry Dept., Rerrich B6la t6r 1, 6720 Szeged, Hungary dLaboratoire de RMN, FUNDP, 61 Rue de Bruxelles, 5000 Namur, Belgium Up to three Fe/u.c. could be introduced into the MFI framework in fluoride-containing media. The presence of Fe in tetrahedral framework position is shown by both the white colour of the samples and the isomer shift in M6ssbauer spectra (IS<0.3 mm/s). During calcinations some framework Fe atoms leave the structure. The crystal morphologies and the kinetic data show that the cations exert specific effects in the stabilization of the crystals under development.
339
04-P-18 - Synthesis and characterization of Co-containing zeolites of M F I structure E. Nigro a, F. Testa a, R. Aiello a, P. Lentz b, A. Fonseca b, A. Oszko c, P. Fejes d, A. Kukovecz d, I. Kiricsi d and J. B.Nagy b ~Dipartimento di Ing. Chimica e dei Materiali, Univ.della Calabria, 1-87030 Rende (Cs), Italy bLaboratoire de RMN, FUNDP, B-5000 Namur, Belgium ~Institute of Solid State and Radiochemistry, University of Szeged, H-6720 Szeged Hungary dApplied Chemistry Department, University of Szeged, H-6720 Szeged Hungary Co-containing zeolites of MFI structure were synthesized using alkaline media. The orthorhombic-monoclinic symmetry transition suggests that at least the Co(II) ions occupy tetrahedral framework positions. The XPS data clearly show that the samples contain both framework tetrahedral and extraframework octahedral Co(II) ions at ion exchange positions.
340 13 - F r a m e w o r k s and Acid Sites (Thursday) 13-P-05 - In-situ F T I R studies of the acidity of H3PWl2040 and its porous salts. Interaction with H20, NH3 and pyridine N. Essayem(a), A. Holmqvist(a), G. Sapaly(a), J.C. V6drine(b) and Y. Ben T~arit(a)
(a)Institut de Recherches sur la Catalyse, Villeurbanne, France, essayem @catalyse.univlyonl fr; (b)Leverhulme Centre for Innovative Catalysis, Liverpool, United Kingdom. The dehydration-rehydration mechanism of H3PWI2040, has been investigated by insitu IR spectroscopy. Protonated water clusters (H20)nH + are observed both on the pure non-porous acid and on its acidic porous/mesoporous salts. Further dehydration induces the decomposition of these protonic species and leads to the formation of hydroxyl groups. Strong modifications of the vibration bands of the Keggin unit occur simultaneously. Adsorption of probe molecules such as water, ammonia and pyridine has been performed on samples dehydrated at different temperatures. The adsorption of pyridine over the pure acid H3P generated a peculiar IR spectrum. On the contrary pyridine adsorption on the acidic salt gave rise to the regular pyridine vibrations. 13-P-06 - D y n a m i c s of p-nitroaniline in the micropore of zeolite Z S M - 5
studied by solid-state NMR S. Hayashi and Y. Komori National Institute of Materials and Chemical Research, [email protected], Japan Zeolite ZSM-5 with a high [Si]/[A1] ratio containing 3 to 4 p-nitroaniline (p-NA) molecules per unit cell has been studied by solid-state NMR. 29Si NMR spectral change and detection of the 29Si CP signals after incorporation ofp-nitroaniline demonstrate that the molecules locate in the micropores. 13C CP/MAS NMR spectra of p-NA in ZSM-5 show line broadenings in two C-H signals, which is related with motions of the benzene ring. The frequency of the motion is of the order of 50 kHz, which is comparable to the strength of the IH decoupling field. 2H NMR spectra demonstrate that 180 degree flip of the benzene ring around the C2 axis of the molecule takes place, whose frequency is of the order of 100 kHz at room temperature. 13-P-07 - The use of microcalorimetry to study the effects of post-synthesis treatments on the modification of the acidity of s e v e r a l HY-type zeolites A. Auroux (a) and M.L. Occelli (b)
Institut de Recherches sur la Catalyse, Villeurbanne, France, [email protected]; b MLO Consulting, Atlanta, USA The effects on acidity of post-synthesis treatments on HY-type zeolites have been investigated using NH3 adsorption calorimetry and 29Si and 27A1 NMR. The reaction of aqueous (NH4)ESiF6 solutions with NHaY can yield HY crystals with a Si-enriched framework free from measurable non-framework A1 species in which T(3Si, IA1)/T(4Si,0A1) > 1.0. LZ-210 type crystals with Si/A1=3.1-4.4 have greater acid site density and contain more acid sites with strength > 100 kJ/mol than the reference LZY-82. Steam-aging causes a drastic decrease in acid sites density. However, in the temperature range (760-815~ investigated, the strength of the strongest acid sites in the reference LZY-82 remains practically unaffected after hydrothermal treatment. a
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1 3 - P - 0 8 - ESR investigations of the catalytic properties of Lewis acid sites in H-mordenite T.M. Leu and E. Roduner Institut fiir Physikalische Chemie der Universitdit Stuttgart, Germany, e. roduner@ipc, uni-stuttgart. de The formation and the properties of Lewis acid sites (LAS) in the zeolite H-MOR were investigated by means of ESR spectroscopy through the observation of the radical cation formed upon adsorption of 2,5-dimethylhexa-l,5-diene (DMHD). The following facts have been established: (i) LAS which bind ammonia are not the sites which are responsible for the formation of radical cations. (ii) The amount of DMHD + formed is directly related to the partial pressure of molecular oxygen present in the system. (iii) The addition of oxygen to Hmordenite containing DMHD+'leads to a superoxide radical anion; furthermore, there is strong evidence for a catalytic process involving DMHD+as a radical intermediate in the oxidation of DMHD.
13-P-09- External surface acidity of modified zeolites: ESR via adsorption of stable nitroxyl radicals and IR spectroscopy A.B. Ayupov a, G.V. Echevsky a, E.A. Paukshtis a, D.J. O'Rear b and C.L. Kibby b a Boreskov Institute of Catalysis, Ak. Lavrentieva Av. 5, Novosibirsk, 630090, Russia b Chevron Research and Technology Co., 1O0 Chevron Way, Richmond, CA 94802, USA The external surface Br~3nsted and Lewis acidity of modified zeolites were characterized by FTIR of OH groups and adsorbed CO molecules and ESR of adsorbed nitroxyl radicals. The catalytic properties of the samples were tested in reactions of aromatics conversion: toluene, pseudocumene, and triisopropylbenzene. The correlation between acidity and catalytic activity has been found and discussed. The three methods of external surface characterization can lead to the entire view on zeolite acidity.
13-P-10 - Very strong acid site in HZSM-5 formed during the template removal step; its control, structure and catalytic activity A. Kohara, N. Katada and M. Niwa Tottori University, Koyama, Tottori 680-8552 Japan mikiniwa@chem, tottori-u.ac.jp, Fax +81-857-31-5256 Conditions of a step for template molecule removal affected strongly the concentration of very strong acid site in HZSM-5. Treatment with ammonia water at ca 373 K was also studied as a procedure to affect the solid acidity, and a similarity of acid sites created by both methods was identified. From the quantitative measurements of acid sites, it was found that the very strong acid site consisted of two A1 cations. Catalytic activity for octane cracking was enhanced by the presence of very strong acid site.
342
13-P-I1- Correlation between ~B NMR isotropic chemical shifts and structural parameters in borates and boro-silicates J. P16vert, F. Di Renzo and F. Fajula
Ecole Nationale Sup~rieure de Chimie de Montpellier, Franc. [email protected] liB MAS NMR has been performed for a variety of borates and boro-silicates. Boron atoms in tetrahedral coordination exhibit sharp resonance lines. The l~B isotropic chemical shift displays dependence as a function of framework geometry parameters such as the mean angles and the mean distances . Such correlation can be useful to characterize the boron site in disordered zeolites.
13-P-12 - Investigation of the paramagnetic effect of oxygen in the 23Na MAS N M R and 23Na MQMAS N M R spectra of LiNaX R.J. Accardi (a), M. Kalwei (b) and R.F. Lobo (a)
a Center for Catalytic Science and Technology, Department of Chemical Engineering, [email protected], University of Delaware Newark, DE 19716, USA. b Institute for Physical Chemistry, University ofMfinster Mfinster, Germany 48149. The paramagnetic effects of oxygen molecules on the site III sodium cations in zeolite LiNaX (~70% Li; ~30% Na) were investigated using variable temperature 23Na MAS NMR and 23Na MQMAS NMR spectroscopy. The presence of the oxygen caused a down-field paramagnetic shift for the site III resonance, although smaller than what was expected. 23Na MQMAS NMR was used to calculate isotropic chemical shifts and 2 na order quadrupolar shifts. The quadrupolar shifts of the room temperature sodium resonance remain the same irrespective of the presence or absence of physisorbed oxygen, however, the quadrupolar shift was found to increase at lower temperatures.
13-P-13 - Characterization of acidic sites in HY and LaY zeolites by laserinduced fluorescence of adsorbed quinoline A. Lassoued, J. Thoret, P. Batamack, A. G6d6on and J. Fraissard
Laboratoire de Chimie des Surfaces, UPMC-CNRS, ESA 7069, 4 place Jussieu, 75252 Paris cedex 05, E-mail.'[email protected], Fax : 33.(0)1.4427.5536, France. We report the characterization of acidic sites in HY zeolite, dealuminated or not, and Y zeolites exchanged with lanthanum (LAY), by the laser-induced fluorescence (LIF) method using an N-heteroaromatic base, quinoline, which is adsorbed on the surface and photoexcited at 240 nm. Spectra of quinoline reveal interactions between the adsorbate and surface sites. Unstructured broad bands with lifetimes less than 1 gsec are observed in all samples. Strong Bronsted acid sites interact with quinoline to form the quinolinum ion, that ion being revealed by a band peaking at 390 nm. The acidity of LaY samples is a function of the La 3+ exchange rate; this was fast highlighted by LIF spectroscopy.
343
13-P-14 - D y n a m i c behaviour of acetonitrile molecules adsorbed in ALPO45 and S A P O - 5 studied by solid N M R method S. Ishimaru, M. Ichikawa, K. Gotoh and R. Ikeda
Department of Chemistry, University of Tsukuba, Tsukuba 305-8571, Japan We studied characteristics of micropores in molecular sieves A1PO4-5 and SAPO-5 by observing IH and 2H NMR to detect dynamic behaviour of acetonitrile molecules adsorbed in the pores. From 2H spectra and ~H relaxation times, it was shown that the molecular motion was strongly affected by the existence o f - O H groups on the pore-wall of SAPO-5. The details of the motions are discussed from ~H NMR TI and T2 data.
13-P-15 - D e t e r m i n a t i o n of the Si/A! ratio of faujasite-type zeolites C.H. Rtischer l*, J.-C. Buhl I and W. Lutz 2
llnstitut fiir Mineralogie, Universit~itHannover, Welfengarten 1 Hannover, Germany. *C.Ruescher@mineralogie. uni-hannover,de 2WITEGA Angewandte Werkstoff-Forschungg. GmbHBerlin, Germany Zeolites Y dealuminated by Si/A1 substitution using SIC14 (DAY-S) and dealuminated thermochemically in steam (DAY-T) were investigated by X-ray powder diffraction, infrared spectroscopy and wet chemical methods. The dependence of lattice constants (a) on the molar ratio x = (I+Si/A1) z show non-ideal solid solution behaviour. In a first approximation the change in a (in nm) can be described as: a = 0.187x+2.412, for 0.1 < x < 0.5. For x < 0.1 the change in lattice constant saturates towards a = 2.425 nm. A similar shift in the double ring mode (WDR)is observed, tailing off.
13-P-16 - Theoretical investigation toluene adsorbed on zeolite X
of the chemical shift anisotropy
of
A. Simperler (a), A. Philippou (b), D.-P. Luigi (b), R.G. Bell (a) and M.W. Anderson (b)
a The Royal Institution of Great Britain, London, United Kingdom, [email protected] b UMIST Centre for Microporous Materials, Manchester, United Kingdom Adsorption of toluene on zeolites Li-X, Na-X, K-X, Rb-X, and Cs-X has been investigated with quantum chemical methods. Calculations of geometries, Mulliken partial charges, and 13C chemical shift parameters of clusters representing the catalytically active site are presented. The polarisation of the toluene carbons is the first step in alkylation reactions catalysed by zeolites and, at an early stage, will influence the outcome of the reaction. We show the simultaneous influence of the Lewis acidic cation and the basicity of the zeolite is responsible for altering the electron distribution within the toluene and thus affecting the outcome of an alkylation reaction.
344 13-P-17 - Acid properties of dexydroxylated ferrierites studied by IR spectroscopy J. Datka, B. Gil and K. G6ra-Marek Faculty of Chemistry, Jagiellonian University, 30-060 Cracow, Ingardena 3, Poland. datka@chemia, uj. edu.pl Dehydroxylation was studied as one of methods of "tuning" the acid properties of ferrierite. The concentration and acid strength of both Br6nsted and Lewis acid sites were determined by IR spectroscopy. In non dehydroxylated ferrierite, the concentration of Br6nsted sites was the same as the value calculated from the composition of zeolite. The maximal concentration of Lewis acid sites in the most dehydroxylated zeolite was close to the stoichiometric value: i.e. half of the concentration of Br6nsted sites. The acid strength of OH groups remaining in partially dehydroxylated ferrierites decreased and the strength of Lewis sites formed increased with the extent of dehydroxylation. The hydroxyls inside 10-ring channels and hydroxyls in ferrierite cages are prone to dehydroxylation in the same degree.
13-P-18 - Aluminium species spectroscopy of the active sites
in activated
zeolites:
solid-state
NMR
B.H. Wouters (a), T.-H. Chen (b) and P.J. Grobet (a)
a Center for Surface Chemistry and Catalysis, Department oflnterphase Chemistry, K.U. Leuven, [email protected], Leuven, Belgium b Department of Chemistry, Nankai University, Tianjin, 300071, PR China Aluminium species in activated zeolites has been studied by solid-state NMR spectroscopy. Framework A1-OH defect species are at the origin of reversible tetrahedral-octahedral transformation in mild calcined zeolites. Depending on the calcination degree, the 30 ppm line in the 27A1 MAS NMR spectra of zeolites is a superposition of deformed tetrahedrally coordinated and penta-coordinated AI species.
13-P-19- Aluminium distribution in high silica pentasil ring zeolites B. Wichterlov~i, J. D~de6,ek, Z. Sobalik and J. 12ejka
J. Heyrovsl@ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic;cejka@3"h-inst.cas.cz Distribution of aluminium in the framework of ZSM-5 and Beta zeolites, represented by "A1 pairs" [A1-O-(Si-O)I,2-A1] and "single A1 atoms" far distant from each other, is estimated from the distribution of divalent Co ions at the individual cationic sites, as obtained from the Co(II) Vis spectra, and the changes in the concentration of OH groups and Lewis sites due to Co(II) exchange, monitored by FTIR. It is shown that the distribution of framework A1 is not random, but it is affected by the concentration of aluminium and procedure of zeolite synthesis.
345
1 3 - P - 2 0 - Effects of hydration on AIPO4-14 and AIPO4-18 structures: a~p M A S a n d 27A! 3 Q - M A S N M R s t u d y b C. V. Satyanarayanaa, R. Gupta, K. Damodaran, S. Sivasankera and S. Ganapathy b*
aCatalysisDivision bPhysical Chemistry Division,[email protected], NCL, Pune, India Structural transformations occurring in A1PO4-14 and A1PO4-18, upon calcination and rehydration, have been studied by 31p and 27A1 MAS/3Q-MAS NMR spectroscopy. Isotropic signals obtained from 31p MAS and 27A1 3Q-MAS aid in the direct detection of number of in equivalent T-sites, which could be assigned based on the correlation of the isotropic shifts with mean T-O-T angle. In calcined samples where only tetrahedral P and AI environments exist, AIPO4-18 results clearly show a constrained geometry with minimal tetrahedral distortion for the PO4 and AIO4 structure building units. Signal multiplicity in 3~p and 27A1 spectra of calcined-rehydrated samples of AIPO4-14 and -18 suggest that both respond to hydration in a similar fashion to yield structures with lower space group symmetry.
13-P-21 - Comparative study of the acidity of the structurally related faujasite type zeolites: FAU, EMT and ZSM-20 H. Kosslick (a), R. Fricke (a), H. Miessner (b), D.L. Hoang (a) and W. Storeck (c)
a Institute of Applied Chemistry Berlin-Adlershof kosslick@ aca-berlin.de, Germany b Institute of Environmental Technologies, I. U. T, [email protected], Germany c Federal Institute of Materials Research and Testing (BAM),Berlin, Germany Acidic properties of EMT and FAU type zeolites as well as their intergrowths with similar A1 content, which contain the same structural subunits but differ in stacking, have been studied by different physico-chemical methods like NH3-FTIR. Small finestructure differences have been found which might be the origin of different strengths of acid sites. Slight variations in the acidity of Bronsted acid sites are indicated by the low frequency shift of the OH stretching vibration band of hydroxy groups which are located in the large cavities. In consequence, the protonic acidity is slightly enhanced in the following order: HFAU < HZSM-20 < HEMT.
13-P-22 - The effect of flexible lattice aluminum in zeolites during the nitration of aromatics M. Haouas (a), A. Kogelbauer (a,b) and R. Prins (a)
a Laboratory of Technical Chemistry, Swiss Federal Institute of Technology (ETH), Zurich, [email protected], Switzerland," b Department of Chemical Engineering, Imperial College of STM, London, U.K. The nitration of toluene with nitric acid and acetic anhydride with zeolite catalysts was studied by means of multi-nuclear solid-state NMR spectroscopy in order to explain the enhanced para-selectivity observed with zeolite beta. The reversible transformation of framework aluminum from a tetrahedral into an octahedral environment was revealed by 27A1 NMR upon interaction of the zeolite with the different components of the nitrating system. The flexibility of the lattice seems to play an important role in the regio-selectivity of nitration catalyzed by zeolites.
346
13-P-23 - Characterization of acidic sites in zeolites by heteronuclear double resonance solid state NMR S.B. Waghmode, A. Abraham, S. Sivasanker, J.P. Amoureux a and S. Ganapathy* National Chemical Laboratory, Pune 411 008, India LDSMM, CNRS-8024, Universite de Lille, F-59655, France The structural characterization of Br0nsted acid sites in zeolites can be investigated through heteronuclear double resonance NMR experiments under Magic Angle Spinning (MAS). With these experiments, we have recoupled the 1H-27AI heteronuclear dipolar interactions by using the Rotational Echo Adiabatic Passage DOuble Resonance (REAPDOR) technique. The signal evolution was followed and monitored under MAS and the REAPDOR fraction was experimentally measured. Its time evolution is shown to reflect the differences in Br0nsted acidity of three well known zeolites, namely, LTL, LTY and MOR.
13-P-24- Measurement of M Q M A S heteronuclear correlation spectra in microporous aluminophosphates C. Fernandez (a) and M. Pruski (b). a) Laboratoire ale Catalyse et Spectrochimie, CNRS UMR 6506, ISMRA/Universit6 de Caen, France; b) Ames Laboratory, Iowa State University, Ames, USA Christian. Fernandez@ismra. ~. We present a solid-state nuclear magnetic resonance (NMR) experiment that allows the observation of a high-resolution two-dimensional heteronuclear correlation (2D HETCOR) spectrum between aluminum and phosphorous in aluminophosphate molecular sieve VPI-5. The experiment uses multiple quantum magic angle spinning (MQMAS) spectroscopy to remove the second order quadrupolar broadening in 27A1 nuclei. The magnetization is then transferred to spin-l/2 nuclei of 31P via cross polarization (CP) to produce for the first time isotropic resolution in both dimensions.
13-P-25 - FTIR studies of the interaction of aromatic and branched aliphatic compounds with internal, external and extraframework sites of MFI-type zeolite materials T. Armaroli (a), A. Guti6rrez Alejandre (b), M. Bevilacqua (a), M. Trombetta (a), F. Milella (a), J. Ramirez (b) and G. Busca (a). a DICheP, Universith di Genova, icibusca@csita, unige, it~ Italy b UNICAT, UNAM, [email protected], Mexico D.F, Mexico The interaction of different nitriles (acetonitrile, pivalonitrile and benzonitrile), of branched aliphatic compounds (2,2-dimethylbutane, tert-butyl-alcohol, methyl-tert-butylether, methyl and dimethylcyclohexanes) and of aromatics (benzene, toluene, ortho-, meta- and paraxylene, pyridine, picolines and lutidine) has been studied over four different ZSM5 zeolites, over silicalite-1 and titanium silicalite-1 and over boralite BOR-C. Internal, external and extraframework sites have been characterized and the access to the cavities discussed.
347
1 4 - Frameworks, Cations, Clusters (Thursday) 14-P-06 - Relaxation processes of Na ion in dehydrated Nal2-A zeolite T. Ohgushi and K. Ishimaru
Department of Materials Science, Toyohashi University of Technology, ohgushi@tutms, tut. ac.jp, Japan. Relaxation processes caused by Na § ion in Nala-A zeolite were studied by the dielectric technique. Two loss peaks (two relaxations) were observed in the dehydrated state, and were simultaneously influenced by the water adsorption in the extremely low vapor pressure or the extremely low adsorbed amount. From the way of the influence and a character in the cation distribution of the zeolite, both relaxations were related to the movements of Na + ion on the site near the 4-membered oxygen ring (4MR). It was concluded by considering the arrangements of some cation sites around 4MR that the loss observed in the higher frequency region was caused by the jump of Na § ion between 4MR and 6MR, and the loss in the lower frequency region by the jump ofNa + ion between 4MR and 8MR.
14-P-07 - Adsorption of DTBN at monovalent cations in zeolite Y as studied by electron spin resonance spectroscopy M. Gutjahr, W. B6hlmann, R. B6ttcher and A. P6ppl University of Leipzig, poeppl@physik, uni-leipzig, de, Germany. One major challenge in the research of microporous materials is the spectroscopic characterization of acid sites. A promising approach is their complexation with paramagnetic probe molecules and the subsequent characterization of the adsorption complex ESR techniques. We used the continuous wave ESR method and modem high resolution pulsed ESR techniques such as hyperfine sublevel correlation spectroscopy to study adsorption complexes formed by paramagnetic Di-tert-butyl nitroxide probe molecules and zeolite cations Li+, Na +, K +, Cs+ in Y zeolites. These investigations allow a determination of the geometrical structure of the adsorption complexes and provide information about the influence of the electronegativity of the various acid sites on the electron density distribution.
14-P-08 - Nature of the active sites of Mo-containing zeolites. XANES studies at Mo K and Llll-edges F.G. Requejo (a,b), E.J. Lede (a), L.B. Pierella (c) and O.A. Anunziata (c)
a Dto. Fisica, Fac. Cs Ex, UNLP and IFILP (CONICET), La Plata, Argentina b Present address." Material.Sience Division., LBNL, Berkeley, CA, USA c centro de Investigaci6n y Tecnologia Quimica(CfTe), UTN-FC-Cordoba-Argentina. Molybdenum catalysts, prepared by incipient wetness impregnation of ammonium-MFI, MEL and BEA zeolites, have been studied by XANES at the Mo L2,3-edge and FTIR. The catalytic activity shows on the nature of Mo species. Due to the splitting at Mo La-edges obtain by XANES, Mo atoms are mainly in tetrahedral surrounding in the samples. Linear XANES fit provide information about concentration of Mo-sites related with their coordination. Differences between linear XANES fits at L3 and K-edges can be attributed to different measurement conditions, indicating different of Mo-sites according their hydration capability.
348
14-P-09 - EPR studies on nitrogen monoxide in zeolites H. Yahiro (a), N. P. Benetis (b), A. Lund (b) and M. Shiotani (c)
(a) Faculty of Engineering, Ehime University, Matsuyama, [email protected], Japan. (b) Chemical Physics Laboratory, 1FM LinkOping University, LinkOping, Sweden (c) Faculty of Engineering, Hiroshima University, Higashi-Hiroshima, Japan Nitrogen monoxide (NO) introduced into Na-A(Na-LTA), Na-mordenite(Na-MOR), and NaZSM-5(Na-MFI) zeolites was studied by X-band-EPR measurements. The EPR spectra of NO introduced into Na-LTA revealed the presence of two monoradicals with different rotational rates. The rotational motion of the NO monoradical formed in Na-LTA differed from that in Na-MOR and Na-MFI. A (NO)2 biradical was present in Na-LTA, while it was absent in the calcium ion-exchanged A-type zeolite, indicating that the pressure of Na + is essential for the (NO)2 biradical formation.
14-P-10 - Evidence of partially broken bridging hydroxyls in molecular sieves from IH MAS spin echo N M R spectroscopy T.-H. Chen (a,b), B.H. Wouters (b) and P.J. Grobet (b)
aDepartment of Chemistry, Nankai University, Tianjin, 300071, PR China bCenterfor Surface Chemistry and Catalysis, KU Leuven, Kardinaal Mercierlaan 92, B-3001 Heverlee (Leuven), Belgium, Piet. [email protected]. be By spin echo editing NMR method, combined with the lH{27Al}spin echo double resonance, a new IH signal was found in the thermally treated molecular sieves, reflecting the complexity of hydroxyls as well as the aluminum state in the dehydrated state. It represents an initial stage of the dehydroxylation, or may be related with the initial stage of dealumination.
14-P-11 - Structure change of molecular sieve SAPO-37 at high temperature studied by 27A! MQ MAS N M R T.-H. Chen (a,b), B. Wouters (b) and P. Grobet (b)
aDepartment of Chemistry, Nankai University, Tianjin, 300071, PR China bCenterfor Surface Chemistry and Catalysis, KU Leuven, Kardinaal Mercierlaan 92, B-3001 Heverlee (Leuven), Belgium, [email protected] When SAPO-37 was calcined at 1173 K, Si atoms become mobile and detached from the framework to aggregate to form polymorph silica, while AI-P dense phase was formed, corresponding to a new AI signal which can be distinguished by the 27A1 MQMAS spectrum. The move of atoms in SAPO-37 is the start of the collapse of the framework.
349
14-P-12 - Effects of molecular confinement on structure and catalytic behaviour of metal phthalocyanine complexes encapsulated in zeolite-Y S. Seelan, D. Srinivas*, M.S. Agashe, N.E. Jacob and S. Sivasanker National Chemical Laboratory, Pune 411 008, India, [email protected] Metal phthalocyanine complexes (MPc; M = V, Co and Cu) encapsulated in zeolite-Y were prepared by "in-situ ligand synthesis" and characterized by chemical and thermal analyses and FT-IR, diffuse reflectance UV-vis and EPR spectroscopic techniques. The studies provided evidence for the encapsulation of MPc inside the supercages of zeolite-Y. The Pc moiety distorts from square planarity as a consequence of encapsulation. The encapsulated complexes exhibited enhanced styrene epoxidation activity with tert-butylhydroperoxide compared to the neat complexes in homogeneous medium. The activity and product selectivity of the encapsulated complexes varies with the central metal atom.
14-P-13 - Investigations on isomorphous substitution and catalytically active centres in MeAPO-31 (Me = Mn, Co, Zn, Ti) N. Novak Tusar (a), A. Ristic (a), A. Ghanbari-Siahkali (b), J. Dwyer (b), G. Mali(a), I. Arcon (c) and V. Kaucic (a) a National Institute of Chemistry, Ljublj'ana, [email protected], Slovenia; b Centre for Microporous Materials, UMIST, Manchester, UK; c Nova Gorica Polytechnics, Nova Gorica, Slovenia An incorporation of manganese(II), cobalt(II), zinc(II) and titanium(IV) into the framework aluminium sites of A1PO4-31 is studied. Isomorphous aluminium substitution with cobalt and zinc was confirmed from static 3~p NMR spectrum and 31p MAS NMR spectrum, respectively. UV-VIS and XANES spectra revealed a partial oxidation of framework manganese(II) into manganese(III) in calcined MnAPO-31 and thus a presence of redox centres in the product. The generation of acidic sites (Bronsted and Lewis) in MeAPO-31 was supported by ammonia adsorption/desorption analysis. Strength of acid sites in the studied catalysts decreases as following: MnAPO-31 > CoAPO-31 > ZnAPO-31. Titanium(IV) is present in TAPO-31 as anatase and it is not incorporated into framework sites of AIPO4-31.
14-P-14 - A comparative study of Ti 4+ sites in titanium silicalite (TS-I) synthetized by different methods N.G. Gallegos, A.M. Alvarez, J.F. Bengoa, M.V. Cagnoli, S.G. Marchetti and A.A. Yeramian CINDECA, Fac. Cs. Exactas, Fac. Ingenieria, U.N.L.P., CIC, CONICET., [email protected]; Calle 47 N ~ 257 (1900) La Plata, Argentina. Three TS-1 zeolites were prepared by three different methods. In order to determine that all of them are "well manufactured", DRX, IR, SEM and DRS were used. The jointly use of probe molecules (H202 and C6H6) and DRS allowed us to detect differences in the population of the named "closed" and "open" Ti 4+ sites and in their geometries in the three zeolites. These differences lead to distinct catalytic behavior when these solids are tested in the oxidation of benzene with H202.
350
14-P-15 - Behaviour of F e ( l l l ) ions in Y zeolites in the presence of Cu(II) and Ag(I) ions: an ESR study A.L. Kustov (a), E.E. Knyazeva (a), E.A. Zhilinskaya (b), A. Aboukais (b) and B.V. Romanovsky (a)
a Chemistry Department Moscow State University, Moscow, V-234, Russia, bvromanovsky@mail, ru b Laboratory of Catalysis and Environment, EA 2598, Littoral University, 59140 Dunkerque, France, [email protected] Quenching effect of Cu(II) and Fe(III) paramagnetic ions when both present within NaY large cages is evidenced. On the contrary, the presence of the same quantity of diamagnetic Ag(I) ions in the NaY zeolite did not influenced on the EPR patterns of Fe(III). Observed quenching effect is supposed to be explained caused by the strong dipole-dipole interaction of paramagnetic species. Also, the catalytic activity of Fe-containing zeolite in methanol oxidation decreases after loading a Cu compound.
14-P-16 - FT-Raman spectroscopic studies of host-guest interactions in zeolites Y. Huang,J.H. Leech and R.R. Poissant
University of Western Ontario, Department of Chemistry, London, ON, Canada N6A 5B7 FT-Raman spectroscopy is a powerful technique for investigating host-guest interactions in zeolitic systems via monitoring the guest species. In this presentation, we report our recent results on the investigations of host-guest interactions in two aspects of zeolite chemistry: (1) examining the dynamic and conformational properties of several closely related alkylcyclohexanes including cyclohexane, methylcyclohexane and trans-l,4-dimethylcyclohexane adsorbed inside ZSM-5 framework and (2) probing the reactivity of organometallic species such as (rl6-benzene)tricarbonylchromium(0) on the surface of zeolite Y.
14-P-17 - High-temperature MAS N M R investigation of the mobility of cations and guest compounds in zeolites X and Y M. Hunger, A. Buchholz and U. Schenk
Institute of Chemical Technology, University of Stuttgart, D-70550 Stuttgart, Germany By high-temperature 23Na MAS NMR spectroscopy could be shown that the rapid exchange of sodium cations in dehydrated zeolite Na-Y starts at ca. 573 K and is characterized by an activation energy of EA = 20+2 kJ/mol. The ra~3id exchange of cesium cations in dehydrated zeolite CsNa-Y starts at ca. 423 K. Applying Cs MAS NMR spectroscopy, an activation energy for the cesium exchange in zeolite Y equal to that for the sodium exchange was determined. These activation energies are significantly lower than those estimated for cesium exchange processes observed at temperatures of 423 to 773 K for dehydrated zeolites CsNa-Y and CsNa-X impregnated with cesium hydroxide as guest compound (EA ca. 85 to 115 kJ/mol).
351
14-P-18 - Generation of long-lived electron-hole pairs through sorption of Biphenyl into acidic ZSM-5 zeolites I. Gener (a), A. Moissette (a), H. Vezin (a), J. Patarin (b) and C. Br6mard (a) a Universit6 des Sciences et Technologies de Lille, Villeneuve d'Ascq, France Claude. Br~mard@univ-lille 1.fr b Ecole Nationale Sup6rieure de Chimie de Mulhouse, France. The EPR, UV-visible investigations as well as Raman scattering results provide informative clues about the formation and nature of long-lived electron-hole pairs through spontaneous biphenyl ionization upon sorption in the void space of activated ZSM-5 zeolites. The transferred electron is trapped within the framework by electron accepting site, while biphenyl radical cation captures one electron from electron donating sites of zeolite framework to restore BP ground state and causes an electron deficient hole.
14-P-19 - Defects study in microporous materials by HRSEM, H R T E M and diffraction techniques G. Gonzalez*, Z. Lopez* and R. Reichelt** *Laboratorio de Materiales, Centro Tecnol6gico, lnstituto Venezolano de Investigaciones Cientificas, IVIC, Caracas 1020A, Venezuela. e-mail. [email protected]. **Institut fur Medizinische Physik und Biophysik der Universitat Munster, Munster, Germany Control synthesis of MFI, MEL and MFI/MEL intergrowth systems has been performed by a systematic variation of different parameters: SIO2/A1203, template/SiO2, Na20/SiO2, H20/ SiO2, templates ratio (TPABr/TBABr), temperature and crystallization time. The study of the relationship between synthesis parameters, crystal morphology, crystal size and density of defects has been carried out. Detailed characterization has been performed by HRSEM, HRTEM, x-ray diffraction, electron diffraction and sorption measurements.
14-P-20- The effect of the framework structure on the chemical properties of the vanadium oxide species incorporated within zeolites and their photocatalytic reactivity S. Higashimoto a, M. Matsuoka a, M. Che b and M. Anpo a* a Dept. Appl. Chem., Osaka Prefecture University, [email protected], Japan b Laboratoire de R6activit6 de Surface, Universit~ P. et M. Curie, UMR7609, CNRS, France XAFS (XANES and FT-EXAFS) and phosphorescence studies including lifetime measurements of several types of vanadium silicalite catalysts clearly showed the oxidation state and coordination geometry of the highly dispersed V-oxides as well as the local distortion structure of these species in their framework structures. Furthermore, dynamic quenching studies of the phosphorescence by adding reactant molecules showed that the charge transfer excited triplet state of these V-oxides, (V4+ - O-)*, acted as active sites for the photocatalytic decomposition reactions of NO both in the presence and absence of propane, their reactivity being strongly dependent on the framework structure of these catalysts.
352
14-P-21 -Characterization of aluminium and iron sites in MCM-22 J. (~ejka (a), J. D6de~ek (a), J. Kotrla (a), M. Tudor (a), N. Zilkovd (a) and S. Ernst (b)
a J. Heyrovsl~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic; cejka@l'h-inst.cas.cz b Department of Chemistry, Chemical Technology, University of Kaiserslautern, Erwin SchrOdinger Strasse 54, D-67663 Kaiserslautern, Germany Type and distribution of aluminium and iron in the framework of zeolite MCM-22 were investigated using adsorption of d3-acetonitrile, pyridine and 2,6-di-tertbutylpyridine followed by FTIR spectroscopy, sodium ion-exchange and UV-Vis spectroscopy of Co 2+ ions located in cationic positions. Detailed analysis of aluminium and iron distribution among single ions, ion pairs, Br6nsted and Lewis sites and internal and "external" surface is provided.
14-P-22 - Valency and coordination states of iron in FeAPO-11. An in-situ MSssbauer
study K. L~zfir (a), N. Zilkovfi (b) and J. (~ejka(b)
a Institute of Isotope and Surface Chemistry, Chemical Research Center, P.O. Box 77, H1525 Budapest, Hungary; b 3{. Heyrovsl~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejgkova 3, CZ-182 23 Prague 8, Czech Republic; cejka@l'h-inst, cas. cz Distribution of Fe 2§ and Fe 3§ framework ions and their coordinations in FeAPO-11 structure were investigated employing M6ssbauer spectroscopy and X-ray powder diffraction. . . . . Simultaneous stablhzatlon of Fe 2 + and Fe 3 + ions in various coordination states was observed. It was shown that the structure of FeAPO-11 is rather flexible and the coordination of iron strongly depends on the form of pretreatment. Among ferrous ions, facile transition between octahedral and distorted trigonal coordinations was observed.
1 4 - P - 2 3 - Comparative properties of modified HEMT and HY zeolites from
the FTIR study of CO adsorption" effect of the dealumination amorphous debris on the Br~insted acidity
and
O. Cairon (a) and T. Chevreau (b)
a LCTPCM, UMR 5624, rue Jules Ferry, Pau, [email protected], France b Catalyse et Spectrochimie, ISMtL4-Universitd Caen, [email protected] Progressive CO adsorption has been studied by FTIR spectroscopy on two series of acidleached steamed HEMT and HY zeolites with various Si/A1F ratios. Acidity of structural OH groups of steamed hexagonal faujasites was determined and compared with the results already obtained with the cubic series. Moreover, quantitative estimation of Br6nsted acidity of extraframework phase (numbers and strength) was carried out and allowed to complete the comparison between the two structural varieties. Only minor differences were detectable.
353
14-P-24- Raman spectroscopic study of 2,2'-bipyridine sorbed into ZSM5 A. Moissette, C. Brdmard, I. Gener and N. Louchart
Laboratoire de Spectrochimie Infrarouge et Raman, Universit~ des Sciences et Technologies de Lille, 59655 Villeneuve d'Ascq cedex, France, [email protected] Sorption of 2,2'-bipyridine (bpy) into the void space of Mm/nZSM-5 (m = 0, 3, 6; M = Na +, Zn 2+, H +) zeolites was studied by Raman spectrometry. The differences in the spectra obtained from the loaded zeolites have been rationalized in terms of probable conformation within the zeolite channels. It appears clearly that bpy conformation depends on the aluminum content of the framework, nature of cations and zeolite acidity, bpy occluded in silicalite-1 was found to be in the trans conformation. The non bonding interactions between the extraframework Na + cation and occluded bpy stabilize the cisoid non-planar conformer, whereas the coordination bonding between Zn and N atoms constrains the cis planar conformation. In HZSM-5, bpy sorption results in both mono and diprotonation of bpy. 9
9
9
2+
9
14-P-25 - Fractals of silica aggregates Z. Li a, D. Wu a, Y.-H. Sun a*, J. Wangb, Yi Liu b and B. Dong b
aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China bSynchrotron Radiation Laboratory, Institute of High Energy Physics, Chinese Academy of Sciences, P.O.Box 918, Beij'ing 100039, P R China Small Angle X-ray Scattering was used to determine the fractal property of silica aggregates prepared by base-catalyzed hydrolysis and condensation of alkoxides in alcohol. As-produced samples were found to be mass fractals. The fractal dimensions spanned the regime 2.1---2.6 corresponding to more branched and compact structures. Both RLCA and Eden models dominated the kinetic growth under base-catalyzed condition
14-P-26 - Structure of Mo species incorporated into SBA-1 and SBA-3 studied by XAFS and UV-VIS spectroscopies H. Yoshitake, S.H. Lim, S. Che and T. Tatsumi
Yokohama National University, Yokohama, [email protected], Japan Direct incorporation of Mo into template-directed mesoporous silica was carried out via acidic (S'X+I-) route. High Mo-loading was achieved (9 wt%, as MOO3) without destructing the regularity of SBA-1 and SBA-3. The local structural environment of Mo was analysed by UV-vis and EXAFS spectroscopies in comparison with that of Mo-impregnated mesoporous silicas. Edge energy of UV-vis spectra and coordination number obtained from EXAFS showed that Mo agglomerates more easily than in the case of impregnation while the local symmetry of Mo did not differ significantly among the molybdosilicates.
354
14-P-27 - Quantification of electric-field gradients in the supercage of Y zeolites by comparing the chemical shifts of 131Xe (I = 3/2) and 129Xe (I = 1/2) Y. Millot, P.P. Man, M.-A. Springuel-Huet and J. Fraissard Laboratoire de Chimie des Surfaces, CNRS ESA 7069, SystOmes Interfaciaux fi l'Echelle Nanomdtrique, Universit~ Pierre et Marie Curie, 4 Place Jussieu, Casier 196, Tour 55, 75252 Paris Cedex 05, [email protected], France In the supercages of HY zeolite, the difference in chemical shift (Scs(131Xe) - ~cs(129Xe)) of the two NMR-observable isotopes 131Xe, which is sensitive to the electric-field gradient (EFG), and i29Xe, which is not sensitive to EFG, is -5 ~lPm at room temperature. The latter value is due to the second-order quadrupole shift of I Xe and provides us with the EFG generated by the framework of this microporous material: 16.3xl 0 ~9V.m -2.
14-P-28 - Iron species present in Fe/ZSM-5 catalysts prepared by ion exchange in aqueous medium or in the solid state M.S. Batista a, M.A.M. Tortes b, E. Baggio-Saitovich b and E.A. Urquieta-Gonzfilez a Dep. Chem. Eng./UFSCar, S6o Carlos- SP, Brazil. e-mail." [email protected] bBrazilian Center for Research in Physics, Rio de Janeiro, Brazil. The Fe species formed during the preparation of Fe/ZSM-5 catalysts by ion exchange in aqueous medium or in the solid state were studied. XRD, EPR, M6ssbauer spectrocopy (MOSS) and chemical analysis (AAS) were used to sample characterization. The catalysts were evaluated through the propane oxidation in the range from 373 to 773 K. The MOSS data evidenced the presence of Fe +3 species in charge-compensation sites and a more content of hematite (Fe203) in the catalysts prepared in aqueous medium. In the propane oxidation, the activity of the Fe/ZSM-5 can be correlated with the amount of Fe-cationic species, confirming that they are the responsible for the catalytic activity.
14-P-29 - Laser ablation mass spectrometry: a technique for observing zeolite occluded molecules S. Jeong(a), K.J. Fisher(a), G.D. Willett(a) and R.F. Howe(b)* a School of Chemistry, University of New South Wales, Sydney NSW 2052, Australia b Chemistry Department, University of Aberdeen, Aberdeen AB24 3 UE, UK, [email protected] Laser ablation mass spectrometry (LAMS) uses a pulsed laser to destroy zeolite structures, release and ionize molecules occluded within the zeolite pores. High resolution mass spectrometry can then be used to study the ions produced. This paper describes LAMS studies on two well defined model systems: hexamethylbenzene(HMB) adsorbed in NaFAU, and the tetrapropylammonium(TPA) template in MFI. It is shown that LAMS can be used to identify the adsorbed species.
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1 4 - P - 3 0 - Characterisation of TS-I active sites by adsorption of organic probes C. Flego*, A. Carati and M.G. Clerici EniTecnologie S.p.A. [email protected] - S. Donato Mil. (MI) - Italy UV-Vis-IR spectroscopy shows the involvement of Ti sites of TS-1 in the adsorption of oxygenated probes (i-propanol, diethyl ether, propylene oxide, glycols) and pyridine. The interaction affects the IR signal at 3725 cm l, which is tentatively attributed to TiOH groups. In partially hydrated TS-1, lattice Ti is involved in the sorption of organic molecules directly through one OH group and indirectly influencing the environment through the nearest SiOH groups. S-1 shows in the comparison with TS-1 a lower density and a weaker strength of adsorption of the organic probes. The interaction of the probes with Ti sites is reinforced through co-operative H-bonds in MFI zeolitic structure, while in the amorphous mesoporous titanium-silicalite this phenomenon is less relevant.
14-P-31 - NIR FT-Raman spectroscopy on molecular sieves E. L6ffler and M. Bergmann Lehrstuhl Technische Chemic, Ruhr-Universiti~t Bochum, P.O. Box 102148, D-44780 Bochum, Germany The potential of NIR FT-Raman spectroscopy for the investigation of zeolites (vanadylcontaining MFI, TS-1) as well as alumophosphate-based molecular sieves (AEI, CHA, CLO) are described. In Raman spectra of template containing samples bands of the organic species dominate. By dispersive Raman microscopy a spatial distribution in a CoAPO-34 crystal is observed. The Raman spectra allow a very rapid and sensitive detection of anatase formed during thermal treatment of as-synthesised titanium-containing zeolites. Different vanadium species are detected in vanadium-containing ZSM-5.
14-P-32 - Characterization of Zn and Fe substituted mordenite by X A F S M. Dong, J.-G. Wang* and Y.-H. Sun State Key Laboratory of Coal Conversion, Taiyuan, Shanxi, [email protected], P.R. China The local structures of Zn (II) and Fe (III) in the lattice framework of mordenites have been characterized by means of X-ray Absorption Fine Structure. The main absorption structure of the XANES reveals the covalent bonding between the heteroatom and the lattice oxygen atom. The pre-edge structure appeared in XANES spectra of (Si, Fe)-MOR suggests a tetrahedral structure of Fe, which confirms the incorporation of Fe into the zeolite framework. Furthermore, the tetrahedral structure of the heteroatoms in the framework and their coordination distances are determined by using EXAFS technique.
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14-P-33 - Identification of vanadium species in VAPO and V A P S O aluminophosphate by UV resonance raman spectroscopy Jia. Yu, Z. Liu*, Q. Xin and C. Li Natural Gas Utilization & Applied Catalysis Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, P. O. Box 110, Dalian 116023, [email protected], China A sensitive UV resonance Raman spectroscopy has been used to characterize both VAPO-5 and VAPSO-5 aluminophosphate. UV-Raman spectra of VAPO-5 suggest that three different vanadium species exist in VAPO-5, but the framework vanadium species are not observed. However, the framework vanadium species exist in VAPSO-5 and are located in the matrix of framework silica.
14-P-34 - On the interaction of H20 with TS-I: a spectroscopic and ab-initio study A. Damin (a), G. Ricchiardi (a), S. Bordiga (a), F. Bonino (a), A. Zecchina (a), F. Ricci (b), G. Span6(b), F. Villain (c) and C. Lamberti (a)
a Dipartimento di Chimica 1FM, Via P. Giuria 7, 1-10125 Torino, Italy, [email protected] b EniChem S.p.A., Centro Ricerche Novara, "lstituto Guido Donegani d Laboratoire de Chimie lnorganique et Mat~riaux Mol&ulaires ESA CNRS 7071 Paris We report an IR, EXAFS and ab-initio study on the interaction of TS-1 with water. IR spectroscopy shows that water is reversibly adsorbed at RT, indicating a weak interaction between H20 molecules and TS-1. EXAFS has evidenced an elongation of the 4 Ti-O bonds of only 0.03 A upon water adsorption. On a theoretical ground, the adsorption of a water molecule has been investigated on three clusters of increasing size: [Ti(OH)4)], [Ti(OSiH3)4] and [TiOsSi6Hl2]. On the two bigger clusters a binding energy in the range of 10-15 kJ/mol has been obtained. Our study confirms that TS-1 is a rather hydrophobic material.
14-P-35 - Spectroscopic study of the nature of vanadyl groups: influence of the support (SiO2 and All] and SiB zeolites) S. Dzwigaj (a,*), M. Matsuoka (a), M. Anpo (b) and M. Che (a,c)
(a) Laboratoire de R~activit~ de Surface, Paris, France dzwie.ai(i~ccr./ussieu.fr; (b) Department of Applied Chemistry, Osaka Prefecture University, Osaka, Japan," (c) Institut Universitaire de France Diffuse reflectance UV-Visible and photoluminescence spectroscopies have been used to study the local environment of vanadium ions dispersed on the surface of amorphous (SiO2) and crystalline (non-dealuminated A1B and dealuminated SiB zeolites) supports. It is demonstrated that the molecular structure of vanadium (V) species depend strongly on the nature of the support. The application of photoluminescence spectroscopy allows to distinguish in as prepared VSiO2, VA1B and VSiB materials one, two and three kinds of tetrahedral vanadium (V) species, respectively.
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14-P-36 - Characterization of Ni, Pt zeolite catalysts by TEM and EDX M.H. Jordgo and D. Cardoso
Chemical Engineering Department, Federal University orS. Carlos, S6o Carlos-SP, Brazil. Fax." (+55-16) 260-8264. [email protected] and [email protected] Bimetallic bifunctional catalysts containing different proportions of Ni and Pt supported in HUSY zeolite were prepared and characterized by TEM, punctual EDX analysis and n-hexane isomerization. The EDX analysis of the Ni and Pt bimetallic catalysts shows that the metal particles contain both metals and from HRTEM it was observed that the bimetallic particles have crystallographic parameters of metallic nickel. The presence of small platinum amounts in the nickel catalysts produces more active catalysts for the n-hexane isomerization, and presents also higher selectivity for the formation of dibranched hexane than the ones containing only platinum.
14-P-37 - N M R and ESR investigations of alkali metal particles in NaY zeolite F. Rachdi a*and L.C. de M6norval b
~GDPC, UMR 5581 CNRS, UM2, Montpellier, France, [email protected] bLMC30, UMR 5618 CNRS, ENSCM, Montpellier, France, [email protected] NaY zeolite loaded with sodium or rubidium metals vapor phase deposition has been investigated by ESR, 129Xe, 23Na and 87Rb NMR. Exposure of the zeolite to a high Na concentration leads to a single ESR line which is attributed to Na metallic particles inside the zeolite cavities. 129XeNMR spectrum of NaY zeolite loaded with Na shows three lines at 88, 94 and 134 ppm which are interpreted in terms of domains of nonuniformely distributed metal particles. By annealing at 670 K the spectrum collapses to a single line at 120 ppm, characteristic of a narrow particle size distribution. 23Na and 87Rb NMR spectra in the temperature range 260 K-300 K were obtained for Rb loaded NaY zeolite. The observed resonances can be explained by the presence of Na/Rb alloy phase in the zeolite cavities.
14-P-38- Topochemical changes in large MFl-type crystals upon thermal treatment in oxidizing and non-oxidizing atmosphere O. Pachtovfi (a), B. Bernauer (b), J.-A. Dalmon (c), S. Miachon (c), I. Jirka (a), A. Zikfinovfi (a) and M. Ko~ifik (a)
a *J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Praha, [email protected], Czech Republic; b Institute of Chemical Technology, Praha, Czech Republic; c Institute de Recherches sur la Catalyse (CNRS), Villeurbanne, France TPAOH removal from large as syntesized silicalite-1 crystals with internal morphology of 90~ has been investigated in regimes with gas flow in parallel to and through the crystal layer both in absence and presence of oxygen. The void space accessibility of crystals was estimated from sorption isotherms of N2 which exhibited as a rule two steps. The topochemical changes in crystals after a partial template removal were evaluated using light microscopy, ESCA measurements and elemental analysis of organic residues.
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14-P-39- Structure of Fe(III) sites in iron substituted aluminophosphates: a computational and X-ray spectroscopic investigation C. Zenonos(a), A. Beale(a), G. Sankar(a), D.W. Lewis(b), J.M. Thomas(a) and C.R.A. Catlow(a) a Davy Faraday Research Laboratory, The Royal Institution ofGB, [email protected] United
Kingdom; b Department of Chemistry, University College London, United Kingdom We compare the structure of Fe(III) active sites in the small pore FeA1PO-18 and large pore FeA1PO-5 catalysts prepared using appropriate structure directing agents. The present study clearly points out that it is possible to substitute Fe(III) ions for tetrahedrally coordinated AI(III) in the framework of A1PO-5 and A1PO-18 to yield an active and selective oxidation catalysts. The use of atomistic simulations is again proven to provide accurate geometries which, when combined with the analysis of the EXAFS data, yield accurate models for the active sites.
14-P-40 - Possible formation of Cu +2(CO)2( H 20). complexes in a ZSM-5 zeolite prepared by direct synthesis: evidence for the occurrence of Cu+-Cu + pairs? F. Geobaldo 1, B. Onida ~, M. Rocchia l, S. Valange 2'3, Z. Gabelica 2 and E. Garrone l'*
/Dipartimento di Scienza dei Materiali e In~egneria Chimica, Politecnico di Torino, Torino Italy E-Mail [email protected]; Universitd de Haute Alsace, ENSCMu, GSEC, Mulhouse, France," 3LACCO, UMR CNRS 6503, ESIP, Poitiers, France Cu-ZSM-5 zeolite prepared by direct synthesis via a methylamine route show Cu + species as defined as those present in samples prepared by CuC1 vapour exchange. The IR study of the reversible interaction of water with presorbed CO shows a variety of bands, the most plausible interpretation of which is the formation of species (HzO)nCOCu+(OH)Cu+CO(HzO)m (n,m 0,1,2), which suggests the occurrence of Cu + species in pairs.
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22 - A d v a n c e d Materials (Thursday) 22-P-06 - Tailored generation of titanium oxide species within porous Si-MCM-41 P. Prochnow (a), G. Schulz-Ekloff (a), M. Wark (a,b), J.K. Thomas (b), A. Zukal (c) and J. Rathousky (c) a Institute of Applied and Physical Chemistry, University of Bremen, Germany, [email protected]; b Department of Chemistry and Biochemistry, Notre Dame University, USA; c J. Heyrovsky Institute of Physical Chemistry, Prague, Czech Republic It is elaborated, that the generation of titanium oxide species of tailored and uniform size into Si-MCM-41 as host material does not only depend on the amount of titanium compounds added in one step, but also on the repeated addition and hydrolysis of the titanium compound in consecutive steps. Anatase nanoparticles of a well-defined size of up to 3 nm, Ti(IV) oxide oligomers and mononuclear Ti(IV) oxide species, respectively, were generated without a substantial enrichment of titanium oxide particles on the extemal surface of the Si-MCM-41 host. Depending on the size and content of the Ti(IV) oxide species, the fluorescence of co-impregnated dye molecules was statically quenched to varying extent.
22-P-07 - Optical switching with photochromic dye molecules encapsulated in the pores of molecular sieves by in-situ synthesis C. Schomburg (a), D. W~hrle (a), G. Schulz-Ekloff (b) and M. Wark (b) a Institute of Organic and Macromolecular Chemistry, University of Bremen, Germany ; b Institute of Applied and Physical Chemistry, University of Bremen, Germany, mwark@chemie, uni-bremen,de Spiropyran or its configurational isomers (merocyanines), respectively, are incorporated in the supercages of faujasite (NAY, HY and DAY) by in-situ synthesis. Luminescence spectra of the colored isomers indicate the non-aggregated incorporation of merocyanine forms. Photochromism experiments exhibit high quantum yields for the photoinduced switching between the different configurational isomers. The strong retardation of the thermal relaxation rate from the cis isomer to the trans isomer in the faujasite hosts is attributed to an increase of the rotation barriers by the imposed spatial restrictions. A strongly increased stability towards photobleaching is found with respect to spiropyrans stabilized in organic polymers or SiO2 based MCM-41 matrices.
22-P-08 - F o r m a t i o n of carbon nanotubes on various molecular sieves supported metal oxides A.M. Zhang, Q.H. Xu, J.J. Zhao and J.M. Cao Department of Chemistry, Nanjing University, Nanjing, 210093, P. R. China The carbon nanotubes were formed on metal oxide-supported zeolite by the decomposition of acetylene hydrocarbon at 700~ The optimum reaction conditions of growth of nanotubes on various molecular sieve catalysts, including Y, A, MOR, ZSM-5 and MCM-41, were studied. Fe/Co-supported Y zeolite catalyst may be the best catalyst for growth of nanotubes in them. Masses of carbon nanotubes with uniform diameter of about 30 nm were obtained over pretreated Y zeolite. The states of iron in Fe-supported Y catalyst measured by M6ssbauer spectrum during three stages of original, hydrogen reduced and catalytic synthetic nanotubes indicated that the hydrogen generated during the reaction is enough to reduce the Fe(III) to sub-valence active state. The nanotubes of larger diameter may be as the template of GaN growth.
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22-P-09 - Encapsulation of Tb[(CIBOEP)4P](acac) in Si-MCM-41 by the method of ship-in-bottle and its luminescent properties at 77 K Q. Xu(a), Z. Zhao(b), L. Li(a), G. Liu(b), H. Ding(a), J. Yu(a) and R. Xu(a)
a: Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023, People's Republic of China. E-mail:[email protected] b." Chemistry Department, Jilin University, Changchun 130023, People's Republic of China. Tb[5,10,15,20-tetra(para-(4-chlorobenzoyloxy)-meta-ethyloxyphenyl)Porphyrin] (acetylacetone) denoted as Tb[(C1BOEP)4P](acac) has been prepared by encapsulating Yb(acac)3 into (CIBOEP)4P-doped Si-MCM-41. The properties of the samples are studied by ICP, XRD, ESR, UV-vis, XPS and spectrofluorometry. It is found that the assembly has better luminescent properties than the pure complex at 77 K.
2 2 - P - 1 0 - A new adsorbent with magnetic properties based on natural clinoptilolite V. Pode (a), V. Georgescu (b), V. Dalea (a), R. Pode (a) and E. Popovici (b)
a University "Politehnica" of Timisoara, Romania, Email: [email protected] b University "AI. I. Cuza" oflasi, Bvd. Copou No. 11, 6600 Iasi, Romania The present research aimed to use the Romanian volcanic tuff as an adsorbent material with magnetic properties. The magnetic properties were induced by a chemical method for covering the volcanic tuff particles with magnetite. The modified volcanic tuff was synthesized by varying some parameters that could influence the adsorption and magnetic properties. The magnetic characteristics of the samples were investigated by induction using a Howling device. The adsorbent material could be used for pollution abatement in viscous media contaminated by highly toxic metal ions that could be separated afterwards based on their magnetic properties.
22-P-11 - Preparation of microcalorimetric gas sensors with C o A P O - 5 S. Mintova (a), J. Visser (b) and T. Bein (a)
aDepartment of Chemistry, University of Munich, Butenandtstr. 5-13 (E), 81377 Munich, Germany, svetlana, mintova@cup, uni-muenchen, de bFord Research Laboratory, MD 3028, Dearborn, M148121-2053, USA Microcalorimetric sensors were prepared by direct synthesis and impregnation of Co in the AFI type material. The synthesis of the CoAPO-5 samples was performed under hydrothermal conditions in a microwave oven using various concentrations of Co, organic template and different conditions of a microwave irradiation. The resulting powder samples used for further preparation of calorimetric sensors were characterized using XRD, TG, nitrogen sorption and UV-vis spectroscopy. The CoAPO-5 films were formed by a drop coating method and tested as gas sensors toward carbon monoxide and cyclohexane. The temperature-change of the sensors depends on the amount and the location of the Co in the AFI type structure and on the accessible pore volume.
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22-P-12 - Study of cation-exchange properties of an organozeolite V.A. Nikashina, E.M. Kats, I.V. Komarova, N.K. Galkina and K.I. Sheptovetskaja
Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygin str. 19, Moscow 117975, Russia."fax" (095)-938-2054, e-mail" elkor@geokhi, msk. su To evaluate the cation-exchange properties of organozeolite-Clinotsides obtained on the basis of the natural clinoptilolite-containing tufts of Tedzami (Georgia) and Holinskoye (Russia) deposits, an earlier developed method of determining their effective equilibrium and kinetic characteristics including the comparison of theoretical and experimental breakthrough curves was used. The quantitative characteristics of cation-exchange processes were obtained. It is shown that there is significant influence of the modification on the kinetic of the cationexchange on Clinotsides.
22-P-13 - A d v a n c e d electrode materials based on m e s o p o r o u s a l u m i n u m stabilized anatase A. Attia (a), S.H. Elder (b), R. Jir~isek (a), L. Kavan (a), P. Krtil (a), J. Rathousk~, (a) and A. Zukal (a) a J. Heyrovsk~ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolej~kova 3, 182 23 Prague 8, Czech Republic, rathous@/h-inst.cas.cz b The William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, U.S.A. A novel mesoporous molecular sieve was prepared whose framework is composed of anatase nanocrystals stabilized by aluminum. The material was characterized by X-ray diffraction, Raman spectroscopy, nitrogen adsorption and lithium insertion electrochemistry. The faradaic capacity and charge-transfer kinetics is considerably higher that those of analogous structures stabilized by Zr.
22-P-14 - Dye-zeolite assemblies for optical sensing applications J.L. Meinershagen and T. Bein* Department of Chemistry, Ludwig Maximilians Universit~it, Butenandtstr. 11-13 (E), 81377 Munich, Germany. Julia.Meinershagen@cup. uni-muenchen.de The aim of this work is to combine the shape selectivity of zeolites with the chemical sensitivity of solvatochromic dyes; this has been explored for the application of size-selective vapor sensing. Solvatochromic dyes are extremely sensitive to their surrounding environment and display large wavelength shifts in visible and fluorescence spectra reflecting changes in polarity. Dye / zeolite ensembles were prepared by ion exchange and inclusion synthesis as well as direct adsorption. Optical responses to various organic analytes have been measured using visible diffuse reflectance and fluorescence spectroscopy. Fast and reversible optical changes have been observed for a wide range of molecules.
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2 2 - P - 1 5 - A new s o r b e n t based on c l i n o p t i l o l i t e - c o n t a i n i n g tuff modified by polyethylene I.N. Meshkova (a),V.A. Nikashina (b),T.M. Ushakova (a),V.G. Grinev (a) ,N.Yu. Kovaleva (a), A.A. Zaborskii (b), T.A. Ladygina (a) and L.A. Novokshonova (a) ~Semenov Institute of Chemical Physics RAS, [email protected], Russia. bVernadsky Institute of Geochemistry and Analytical Chemistry RAS, [email protected], Russia. Clinoptilolite-containing tuff (CT) dust was modified by the catalytic polymerization of ethylene on the surface of CT particles. The compositions with 3-5wt.% of polyethylene (PE) and 97-95 wt.% of CT were obtained. The thin PE coating formed on the CT particles was permeable to the filtrating water solutions. As a result of encapsulation of the CT particles, the filter properties of this sorbent were improved. The ion-exchange characteristics of the modified CT (powder and pressed tablets) with respect to NH4 + and Sr2+ cations were determined. It was shown that CT dust-PE compositions retained the ion-exchange properties of initial CT.
22-P-16 - M o l e c u l a r sieves from pillaring of s o m e r o m a n i a n bentonite E. Popovici a, I. Bedelean b, D. Pop b, G. Singurel a, D. Macocinschi c and H. Bedelean b
~"Al.I.Cuza" University of Iasi, Romania, [email protected]; b"Babes Bolyai" University of Cluj-Napoca, Romania; c "P.Poni" Institute of Macromolecular Chemistry We report here preliminary results of the physicochemical characterization of a composite material obtained by combining the cethyltrimethylammonium cations clay insertion procedure with the room temperature synthesis of mesoporous materials inside of clay layers. The Romanian bentonite, containing 64% montmorillonite was used. The organic cations are incorporated within the interlayer region of the clay, serving to prop open the layers and to allow incorporation of the silicon source for MCM-41 synthesis. The obtained materials display a high thermal stability and molecular sieve properties.
22-P-17 - Electronic states and a r r a n g e m e n t s of AgI and CuI clusters i n c o r p o r a t e d into zeolite L T A T. Kodaira a and T. Ikeda b aNational Institute of Materials and Chemical Research, Tsukuba, Ibaraki 305-8565, Japan, kodairanimc.jp; bNational Institute for Research in Inorganic Materials, Tsukuba, Ibaraki 305-0044, Japan Both AgI and CuI clusters were successfully incorporated into the cages of Na-type LTA. The maximum loading densities of the AgI and CuI molecules per a-cage were 4.0 and 6.3, respectively. In the optical spectra, the lowest absorption bands of both kinds of clusters show a large shift to the higher energy side compared to that of the original bulks. It was found that the space group of the original Na-LTA, Fm3 c, changed to lower symmetry ones by incorporation of both kinds of clusters. These are determined by the appearance of new reflections in the X-ray powder diffraction patterns. The physical properties of these two kinds of clusters seem to be slightly different. CuI molecules adsorbed sparsely into the cage have the property to aggregate and form a cluster. The CuI clusters have large electron-vibration interaction.
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22-P-18- PbI2 nanoclusters in zeolite LTL: host-guest chemistry and optical properties G. Telbiz(a),O. Shvets(a), V. Vozny(b) and M. Brodyn(b) a. Institute of Physical Chemistry, National Acad. Sci.,Kyiv, [email protected], Ukraine b. Institute of Physics, National Acad. Sci., Kyiv, Ukraine We report on the development of host-guest interaction and optical properties in course of preparation procedures of semiconductor clusters PbI2 in the LTL matrix. For the samples with relatively high PbI2 content the narrow emission peak only slightly blue-shifted from Eex was observed. The gradual disappearance of this peak during the storage of the samples in the air is explained by assuming that originally formed long clusters undergo fragmentation into smaller species.
22-P-19 - Application of the molecular sieves as matrices for the pigments S. Kowalak, A. Jankowska, N. Pietrzak and M. Str6zyk Faculty of Chemistry, A. Mickiewicz University, Poznah, Poland. sko walak~m ain. am u. edu. 191 The uniform intracrystalline voids of the molecular sieves can be employed for encapsulation of molecules containing chromophore groups and they can result in forming pigments. Natural lazurite is a good example of zeolite (sodalite) containing sulfur anion-radicals encapsulated in ]3-cages. We demonstrate here that the above radical can be also introduced into AIPO4 sodalite (A1PO4-20), but the attempts to encapsulate it to zincophosphate sodalite were unsuccessful. The latter structure could, however, accommodate CdS molecules, when they are encapsulated during the dry crystallization of SOD. The organic cation-radicals generated in the MFI structure channels (HZSM-5, H-ferrosilicalite, H-zincosilicalite) as a result of oligomerization of styrene and its derivatives form very stable pigments of various colors.
22-P-20 - Laser dye doped mesoporous silica fibers: host-guest interaction and fluorescence properties G. Telbiz(a), O. Shvets(a), S. Boron(a), V. Vozny(b), M. Brodyn(b) and G.D. Stucky (c) a. Institute of Physical Chemistry, National Acad. Sci.,Kyiv, [email protected], Ukraine b. Institute of Physics, National Acad. Sci., Kyiv, Ukraine," c. Department of Chemistry, University of California,, Santa Barbara, CA, USA Transparent mesoporous fibers with excellent order and parallel pores and doped by laser dye are prepared with good reliability. Influence of the nature of laser dye on the host- guest interaction is shown. Optical properties of Rhodamine 6G and Coumarine 120 embedded in mesoporous fiber waveguide have demonstrated utility for new laser materials, microphotonic devices or microreactors with increasing thermostability of dye component. The opportunity of preparation of the composite materials mesoporous fiber / semiconductor is shown.
364
22-P-21 - Spectroscopic properties of dye-loaded mesoporous silicas of the structural type MCM-41 B. Onida l, B. Bonellil, M. Lucco-Borleral, L. Floral, C. Otero Are~.n2 and E. Garrone l
1Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Italy, [email protected]," 2Departamento de Qu[mica, Universidad de Las Islas Baleares, Palma de Mallorca, Spain. Dye-containing mesostructured silica and zeolitic materials are interesting for their potential application in optical devices and as chemical sensors. Congo Red and Curcumin, two pH indicators, have been incorporated in MCM-41, precursors, which have been characterised by means of X-ray diffraction, UV-Visible and FTIR spectroscopy. Dyes are located in the micellar phase of the silica-surfactant mesophase and their spectroscopic properties confirm that they are in a solvated state, where both surfactant and silica wall may act as a solvent. Dyes maintain their pH indicator properties and are accessible to gases such as HC1 and NH3.
365 27 - Selective Oxidation over Micro- and Mesoporous Catalysts (Thursday)
27-P-06 - Microporous metallosilicates for the oxidation of hydrocarbons: preparation, characterization and catalytic activity U. Arnold (a), R.S. da Cruz (b), D. Mandelli (c) and U. Schuchardt (a).
a Universidade Estadual de Campinas, ulf(-&iqm,unicamp, br, Brazil. b Universidade Estadual de Santa Cruz, Ilh~us, Brazil. c Pontificia Universidade Cat6lica de Campinas, Brazil. Metallosilicates containing Cr, Cu or Mo have been prepared by an acid-catalyzed sol-gel process. Structural information about the silicates were obtained by elemental analysis, TGA, XRD, XRF, N2-physisorption, EPR, UV/VIS and FTIR spectroscopy. The silicates are active catalysts for the oxidation of hydrocarbons with tert-butyl hydroperoxide. Catalyst stabilities with regard to metal leaching during catalytic oxidations were investigated.
27-P-07 - High catalytic activity of Fe (Ill)-substituted aluminophosphate molecular sieves (FeAPO) in oxidation of aromatic compounds X. Meng, Y. Yu, L. Zhao, J. Sun, K. Lin, M. Yang, D, Jiang, S. Qiu and F.-S. Xiao* Dept. of Chemistry, dilin Univ., Changchun 130023, China, E-mail.'[email protected] Iron substituted aluminophosphate molecular sieves (Fe-A1PO4-11, Fe-AIPO4-5 and Fe-VPI5) are catalytically active in oxidations of aromatic compounds such as hydroxylation of phenol, benzene, and naphthol, as well as epoxidation of styrene. Catalytic data show that the activities of Fe-A1PO4-11, Fe-AIPO4-5 are comparable with that of TS-1 in the oxidation of aromatic compounds. Furthermore, Fe-VPI-5 shows high activity in naphthol hydroxylation by H202, while TS-1 is completely inactive due to the small pore size. By comparison of various catalysts, Fe (III) in the framework is considered to be the major active site in the catalytic reactions.
27-P-08 - Selective oxidation of propyl alcohols over zeolites modified with cations of the transition metals A.M. Aliyev, D.B. Tagiyev, S.M. Medzhidova, S.S. Fatullayeva, A.R. Kuliyev, T.N. Shakhtakhtinsky, G.A. Ali-zade and K.I. Matiyev
Institute of Theoretical Problems of Chemical Technology of the Academy of Sciences of Azerbaijan, 370143, Baku, H.david ave., 29, Azerbaijan, E-maih [email protected]. Activity and selectivity of natural (pure and dealuminated clinoptilolite and mordenite) and A synthetic zeolites modified with cations of the transition metals (Cu 2+, Co/+, Cr 2+, Zn 2+ and Pd 2+) have been tested in vapor phase oxidation of iso-propyl and n-propyl alcohols. The efficient catalyst, CuPdH-mordenite has been selected for the oxidation of iso-propyl alcohol to acetone. It has been shown that this catalyst is not efficient in the oxidation of n-propyl alcohol. The catalyst prepared from A synthetic zeolites and containing Pd 2+ and Cu 2+ shows the highest activity in this reaction.
366
27-P-09 - Niobium leaching from the catalysts applied in the sulfoxidation of thioethers with hydrogen peroxide M. Ziolek, A. Lewandowska, M. Renn, I. Nowak, P. Decyk and J. Kujawa
Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 60-780 Poznan, Poland E-mail: [email protected] Micro- and mesoporous materials containing niobium in the framework or extra framework positions were studied in the oxidation of dibutyl sulphide with H202. Leaching of Nb from the solid to the liquid phase was considered. Some of the catalysts prepared via the impregnation with Nb-salts show some leaching of Nb to the liquid phase and the oxidation partially occurs homogeneously in the liquid phase. The reaction proceeds mainly on the catalyst surface when the mesoporous molecular sieves containing Nb in the framework are used.
27-P-10- Biomimetic oxygen transfer by Co and Cu complexes immobilized in porous matrices K. Hernadi (a), I. Pfilink6 (b), E. B6ngyik (a) and I. Kiricsi (a)
a Department of Applied and Environmental Chemistry, University of Szeged, Rerrich B. tdr 1, Szeged, H-6720 Hungary, [email protected]; b Department of Organic Chemistry, University of Szeged, D6m tdr 8, Szeged, H-6720 Hungary Co(II) or Cu(II) histidine or imidazole complexes were immobilized in porous matrices (montmorillonite and MCM-41) via two methods (introduction of preformed complex or complex formation within the ion-exchanged host substances). It was found that immobilization in general and the latter method in particular increased catalytic activity and catalyst life time in the decomposition reactions of hydrogen peroxide relative to the matrixfree complexes. The immobilized materials were characterized by experimental and computational methods and the structures of the guest molecules inside the hosts were also investigated.
27-P-11 - Titanium molecular sieves convert hydrogen peroxide into 102 F.M. van Laar, a D.E. De Vos, a P. Grobet, a J.-M. Aubry, b L. Fiermans c and P.A. Jacobs a
Centre for Surface Chemistry and Catalysis, Leuven, Belgium, [email protected], bEquipe de Recherches sur les Radicaux Libres et l'Oxygbne Singulet, Lille, France," ~Department of Solid State Sciences, Gent, Belgium The interactions of Ti molecular sieves with H202 were investigated with near infrared luminescence spectroscopy to detect the characteristic 1270 nm emission of the short-lived excited singlet molecular oxygen (IO2). From these experiments it was concluded that (1) for all titanium molecular sieves tested, part of the H202 is converted to 102, (2) higher H202 concentrations result in more singlet molecular oxygen, (3) increasing titanium content of the molecular sieve does not result in more 102 production and (4) particularly the hydrophilic (Ti,A1)-13 produces 102 at a high rate.
367
27-P-12 - Propane oxidation on Cu/ZSM-5 catalyst: The effect of copper and aluminum content in the reducibility and in the activity of Cu active species M.S. Batista and E.A. Urquieta-Gonzfilez Dep. Chem. Eng./UFSCar, S~o Carlos- SP, Brazil. e-mail: [email protected] The effect of Cu and A1 content in Cu/ZSM-5 catalysts on the nature of the formed Cu species was studied. The samples were characterized by XRD, AAS, DRIFTS, EPR and Hz-TPR and the activity was checked in the propane oxidation. The samples, irrespective of their Si/A1 ratio and Cu content, show a reduction peak at 210~ which, as evidenced by DRIFT of CO adsorption, corresponds to the reduction of Cu +2 to Cu +l. The reduction peak of Cu +! shifts to higher temperatures with the increase of Si/A1 ratio or with the diminution of Cu/A1 ratio, evidencing that isolated Cu cations present a higher interaction with the zeolite structure. The propane conversion, irrespective of Si/A1 ratio, increased with Cu content in the solid and the TOF number correlated inversely with the Cu/A1 atomic ratio in the zeolite.
2 7 - P - 1 3 - Oxidizing conversion of isobutanol on zeolites S.Zulfugarova
Institute of Inorganic and Physical Chemistry Azerbaijan Academy of Sciences [email protected] Oxidizing conversion of isobutanol on Na, Cu, Co and F e - forms of zeolites of Y, erionite and mordenite types was studied. Zeolite CuY shows the greatest activity in the formation of isobutyric aldehyde (--30%); other samples are suitable for stronger oxidization and dehydration reactions. It was demonstrated by thermodesorption that there is one form of adsorbed oxygen with maximum temperatures of 100 -130~ on Na-erionite and Namordenite. There are high-temperature adsorbed forms of oxygen with maximum temperatures of 120-150, 400-450 and above 600~ on Ni-erionite and Cu-mordenite
27-P-14 - Photocatalytic production of H202 over heterogenized quinone in zeolite J.S. Hwang, C.W. Lee, H.S. Chai and S.-E. Park*
Catalysis Centerfor Molecular Engineering, KRICT, Taejon 305-606, Korea; separk@pado, krict,re. kr The photocatalytic production of H202 from ethanol and 02 is studied by using zeoliteheterogenized quinone catalysts under UV light of 300-400 nm. The photochemical reaction between ethanol an~ 02 initiated by quinone catalysts produces H202 and acetaldehyde equivalently. The/qflinone compounds are heterogenized by both encapsulation method in zeolite pore and anchoring method on zeolite surface. The anthraquinone-2-carboxylic acid (AQCA) catalysts anchored on Pd~ zeolite exhibit enhanced catalytic activity in the formation of H202 from ethanol and 02 as compared with encapsulated quinone catalysts of the Pd~ The anchored AQCA does not leach out and prevent leaching of encapsulated AQCA during the reaction.
368 - Liquid-phase oxidation of cyclohexane chromium and iron ETS-10 materials 27-P-15
in the presence of
A. Valente a, P. Brand~o b, Z. Lin a, F. Gon~alves a, I. Portugal a, M.W. Anderson b and J. Rocha a
a Departamento de Quimica, Universidade de Aveiro, 3810-193 Aveiro, Portugal [email protected], Portugal.
b Department of Chemistry, UMIST, PO Box 88, Manchester M60 1QD, UK The introduction of chromium or iron in microporous titanosilicate ETS-10 provides interesting redox properties for cyclohexane oxidation, using H202 as oxidant, under moderate reaction conditions, that ETS-10 alone does not possess. The main reaction products are cyclohexanol and cyclohexanone. Selectivity to the latter is maximum when acetonitrile is the solvent. The observed reactivity trend for these catalysts towards cyclohexane oxidation decreases when the trapping efficiency of the solvent towards hydroxyl radicals increases. Cyclohexane conversion increases with HEOE/cyclohexane ratios. Metal leaching from these materials during oxidation accounts for loss of catalytic activity upon recycling.
2 7 - P - 1 6 - Effect of oxygen concentration on catalyst deactivation rate in vapor phase Beckmann rearrangement over acid catalysts T. Takahashi and T. Kai
Department of App. Chem. and Chem. Eng., Kagoshima Univ., Kagoshima 890-0065, JAPAN E-mail." [email protected], FAX +81-99-226-8360 The addition of a small amount of oxygen (up to 1000 ppm) in helium was effective to improve the catalytic activity in vapor phase Beckmann rearrangement over HZSM-5 modified with precious metals. The catalyst life time increased using oxygen as the diluent gas. When the amount of oxygen exceeds 1.0 %, the dehydrogenation of the coke precursor is accelerated. The combination of oxygen as the diluent gas and methanol as the diluent solvent was effective to increase the life time of the acid catalysts including an amorphous SIO2-A1203, HZSM-5 type zeolite and porous silica glass.
the role of the titanium active site in the phenol/anisole hydroxylation over titanium substituted crystalline silicates
27-P-17 - On
U. Wilkenh6ner 1, D.W. Gammon 2 and E. van Steen 1
Catalysis Research Unit, 1Dept. Chemical Engineering, 2Dept. Chemistry, University of Cape Town, South Africa Hydroxylation of phenol and anisole was investigated using TS-1, a silanised TS-1 and Alfree Ti-Beta. Pore geometry, solvent, external surface and substrate govern the selectivity of the hydroxylation reaction. In medium pore TS-1 the formation of hydroquinone in phenol hydroxylation is favoured due to the geometric constraint on the formation of catechol in the pores. A similar effect is observed for formation of ortho- and para hydroxy-anisoles in A1free Ti-Beta. Solvents affect activity and selectivity of the hydroxylation reactions through adsorption and co-ordination to the titanium active site. The external surface of TS-1 plays a substantial role in hydroxylation reactions.
369 31 - Environment-Friendly Applications of Zeolites (Thursday)
31-P-05 - Application of sorbing composites on natural zeolite basis for heavy metals contaminated territories rehabilitation W. Sobolev (a), V. Ilyin (b), F. Bobonich (b) and S. B~ir~ny (c)
a S & P Department "Flegmin" ("Sventana" Ltd.), [email protected], Ukraine b Institute of Physical Chemistry of the National Academy of Sciences, Ukraine c University of Miskolc, Institute of Chemistry, Hungary Various compositions of natural zeolites modified for the remediation of soils contaminated by heavy metals and radionuclides are discussed. Modified zeolites are selective adsorbents in respect to bivalent cations including Sr, Cd, Cu, Pb, Zn. Incorporation of modified zeolites into soils reduces the content of lead and other heavy metals by a factor of 4-5 and prevents or diminishes the transport processes from soil into ground water and plant biomass. Using of organo-mineral composites, containing 1-5 % selective sorbent "Zeolite P", is efficient to get ecologically cleaned harvests of corn, bean and vegetable cultures under low contamination.
Investigation of lead removal from wastewater by Iranian natural zeolites using 212pb as a radiotracer
31-P-06-
H. Kazemian(a), P. Rajec(b), F. Macasek(b), and J.O. Kufacakova
a Jaber Ibn Hayan Research Labs., AEOI,, Tehran, IRAN- [email protected] b Faculty of Natural Science, Comenius University, Bratislava, Slovak Republic The uptake of lead from its aqueous solutions (1'10 .5 and 1'10 "2 mol.dm 3, buffered at pH=3.7), by three clinoptilolite-rich tufts from Meyaneh, Firouzkouh, and Semnan; and a natrolite-rich ore from Zahedan (Hormak) region of Iran, was investigated by plotting the ionexchange isotherms and calculating distribution coefficients (Ko). 212 Pb radioisotope was used as a radiotracer. The results provide information on the suitability of the individual zeolites for radioactive and industrial wastewater treatment. The removal of lead by the clinoptilolitesrich tufts was effective and the uptake sequence was Meyaneh > Firouzkouh > Semnan; whereas the take up of lead on the natrolite material was negligible.
3 1 - P - 0 7 - Purification of the waste liquid hydrocarbons using cationexchanged forms of clinoptilolite M.K. Annagiyev, S.G. Aliyeva and T.M. Kuliyev.
Institute of Inorganic and Physical Chemistry, Academy of Sciences of Azerbaijan Republic, Baku. The use of adsorbents obtained on the basis of natural zeolites has a large practical and theoretical importance for different branches of a national economy. Presence of even small quantities of water and iron ions in liquid hydrocarbons of influences negatively upon the quality of the products produced under manufacture of synthetic detergent- sulfonol; corrosion of the industrial and transport equipment takes place too. Usually synthetic adsorbents, which are deficient and expensive are used when drying liquid hydrocarbons.
370
3 1 - P - 0 8 - The use of transcarpathian zeolites for concentrating trace contaminants in water V.O. Vasylechko (a), L.O. Lebedynets (a), G.V. Gryshchouk (a), Y.B. Kuz'ma (a), L.O. Vasylechko (b) and V.P. Zakordonskiy (a). (a) Ivan Franko National University of L 'viv, L 'viv, Ukraine [email protected] (b) Lvivska Polytechnika National Universitat, L 'viv, Ukraine The adsorption properties of Ukrainian Transcarpathian natural zeolites (clinoptilolite and mordenite) and of their chemically and acid-modified forms towards Cd, Cu and chloroform have been investigated. The optimum conditions of concentrating trace contaminants of Cd, Cu and chloroform in water were found. The possibility of the use Transcarpathian zeolites in analyses of water has been demonstrated.
31-P-09 - Ammonia removal from drinking water using clinoptilolite and lewatit S100 H.M. Abd E1-Hady, A. Grtinwald, K. Vlckova:[: and J. Zeithammerova
Civil Engineering Department, Department of Sanitary Engineering, Czech Technical University In Prague - [email protected], fax." 0042 02 24354607, Czech Rep. High concentrations of ammonium in surface water make it unsuitable as drinking water, and this is becoming a major problem in the world. The purpose of this study is to investigate the possibility of removing ammonium from drinking water by means of an ion exchange process. We used one material of natural origin: clinoptilolite and one synthetic material: Lewatit S 100. Experimental results show that Lewatit S 100 has almost 4 and 1.7 times weight capacity for ammonia removal compared to the capacity of clinoptilolite for concentrations 10 and 5 mg NH4+/L respectively, but for 2 mg NH4+/L the weight capacity of clinoptilolite was found to be 1.9 times that of Lewatit S 100.
31-P-10 - Pilot plant of ammonium removal from nitrogen industry waste waters by an Ukrainian clinoptilolite Y.I. Tarasevich and V.E. Polyakov Institute of Colloid Chemistry & Chemistry of Water, [email protected], Ukraine Laboratory studies and industrial tests had shown that to remove the ammonium ions from nitrogen industry waste water, the application of the clinoptilolite is most promising. Sulphuric acid involved in the industrial cycle can be conveniently used for the regeneration of the worked-out clinoptilolite. Optimum conditions for water cleaning using the clinoptilolite filter and for the subsequent regeneration of the filter by sulphuric acid were determined. Eleven sorption/regeneration cycles were performed in industrial conditions; it was shown that the dynamic exchange capacity of clinoptilolite, 0.52 geq/g, remains almost unchanged. The 'hungry' regeneration is shown to be most efficient, enabling the recovery of 60-70% of the clinoptilolite exchange capacity. Cleaned industrial waste water can be used as the make-up water in closed systems of industrial water supply. The worked-off regenerative solutions, after their neutralisation and boiling down, are used as fertiliser.
371
31-P-I I- Croatian clinoptilolite and montmorillonite-rich tuffs for ammonium removal M. Rozic (a) and S. Cerjan-Stefanovic (b)
(a)Faculty of Graphic Arts, Zagreb, Croatia, fax:385~1~2371-077 (b)Faculty of Chemical Engineering and Technology, Zagreb, Croatia Clinoptilolite- and montmorillonite-rich tufts from Croatian deposits were examined to evaluate their ability for ammonium ions uptake. Both tested materials have potential for removing ammonium from waters. However, the montmorillonite-rich tuff is not as effective as clinoptilolite-rich tuff, particularly in the presence of competing Ca 2+ cation. In all experiments, the clinoptilolite-rich tuff exchanged a far more ammonium compared to the montmorillonite-rich tuff.
31-P-12 - Ammonia removal from water by ion exchange using South African and Zambian zeolite samples and its application in aquaculture M. Mwale and H. Kaiser
DIFS, Rhodes University, Grahamstown [email protected], RSA The possibility of improving aquaculture water quality using a Zambian zeolite identified as laumontite and a South African clinoptilolite sample is discussed. These were tested under laboratory conditions and in a fresh water recirculating system. There were significant differences in average ammonia CEC between clinoptilolite (14.94 rag/g) and laumontite (2.77 mg/g). The average cation exchange capacity (CEC) values in the fresh water system (5.80 mg/g and 4.12 mg/g for the 0.7-1.0 and 1.0-1.4 mm particle sizes, respectively) were significantly lower than the column estimates for the same particle sizes. Mass balance of nitrogen (N) indicated that only 22% of the 60% NH4+-N available for adsorption was adsorbed by the zeolite. It was concluded that N budget studies make it possible to determine the amount, nature and effect of the dissolved N load in a fish culture system and on the ion exchange process. The results suggest that both samples can be used in water treatment.
31-P-13 - Permanent storage of chromium in hardened FAU-type zeolite /cement pastes C. Colella, D. Caputo and B. de Gennaro
Dipartimento d'Ingegneria dei Materiali e della Produzione, Universith Federico II, Napoli, Italy Cr removal from wastewater by ion exchange using FAU-type zeolites and the subsequent stabilization of the resulting sludges in a cement matrix is reported. Amounts of 5 g/1 of synthetic faujasite-like zeolite X or 8 g/1 of a faujasite- and phillipsite-rich tuff were able to bring the Cr ~+ concentration in a wastewater of an electroplating plant, below the law limits allowed for discharge in times of practical significance. The compressive strengths of the compacts containing 10% to 75% of zeolitic materials were much higher than the value of 0.44 MPa, suggested by international protocols for handling and landfilling the solidified wastes. Moreover, suitable leaching tests on the hardened pastes resulted in a Cr 3+ concentration in the leachates lower than the law limits allowed for discharge in water bodies (2 mg/1).
372
31-P-14 - Phosphorus removal from wastewater in upgraded activated sludge system with natural zeolite addition J. Hrenovic a, y. Orhan b, H. Btiyiikgting6r b and D. Tiblja~
a
~Faculty of Science, University of Zagreb, Zagreb, [email protected] bOndokuz Mayis University, Environment Eng. Dept.,, Samsun, Turkey- [email protected] A new application of natural zeolites (NZ) in sewage treatment is presented in this paper. The aim of this study was to investigate the enhanced performances of upgraded activated sludge system with NZ addition; particularly as far as phosphorus removal, chemical oxygen demand (COD) and sludge characteristics. Two experimental studies were run; an upgraded activated sludge system with NZ addition and a conventional activated sludge system, run as a control unit. The results point to the possibility of successful phosphorus and COD removal from wastewater by activated sludge bioaugmented with phosphorus accumulating bacteria using NZ as a support material.
31-P-15 - Application of natural zeolites to purify polluted river water M. Okamotoa and E. Sakamotob
aDivision of Earth Sciences, Kyushu International University,, Yahata-higashi ku, Kitakyushu, Japan, [email protected]; b Department of Biological and Environmental Chemistry, Kyushu School of Engineering, Kinki University, Kayanomori, Iizuka, Japan We have attempted to remove the ammonium ions contained in waste river water using natural zeolites in an oxidative atmosphere using a laboratory-scale circulatory apparatus. The ability of zeolites to purify waste-water was compared with that of regular river gravel, which has no ion exchange ability. The results show that Ca-rich mordenite is superior to normal river gravel to purify waste river water polluted by ammonium ions. The decrease of ammonium ions in polluted water was a result not only of ion exchange with calcium ions in zeolite, but also of microbiological oxidation on the surface of zeolite. The ability of natural zeolites to oxidize ammonium ions into nitrate ions is a function of the zeolite contents of minerals and the type of zeolite species.
31-P-16- Elimination of ammonium in seawater by zeolitic products J.M. Lopez-Alcal~. and J.L. Lopez-Ruiz
Centro Andaluz Superior de Estudios Marinos. Departamento de C. Navales. Grupo Zeolitas, C~tdiz University, Puerto Real (Cddiz) Spain. [email protected] The problem of ammonium elimination by zeolites in seawater is studied in this paper. By preparation of new zeolitic products, elimination of 20% of initial ammonium is reached. This is the best result referenced in the literature up to date.
373
32 - Zeolite Minerals and Health Sciences (Thursday) 32-P-06 - Effects of dietary inclusion of natural zeolite on broiler performance and carcass characteristics E. Christaki, P. Florou-Paneri, A. Tserveni-Gousi, A. Yannakopoulos, and P. Fortomaris
Department of Animal Production, Veterinary School Aristotle University of Thessaloniki, 54006 ThessalonikL [email protected], gr, Greece The addition of 2% and 4% natural zeolite (NZ) to broiler diet was studied in a 42-day experiment. Body weight gain, feed consumption, feed consumption ratio, some carcass characteristics and chemical analysis in the muscular mass of breast and legs were determined. The supplementation of 2% NZ in the broiler diet resulted in an improvement of the feed conversion ratio and an increase of body weight, carcass yield as well as linoleic and a-linolenic acid content, without any adverse effect on the other measured parameters. The addition of 4% natural zeolite resulted in a significantly higher feed conversion ratio.
32-P-07Interaction clinoptilolite
studies
between
aspirin
and
purified
natural
A. Rivera (a), L.M. Rodriguez-Albelo (b), G. Rodriguez-Fuentes (a) and E. Altshuler (c)
a Zeolites Engineering Laboratory, University of Havana, jea@in[bmed.sld, cu, Cuba b Organic Materials Laboratory, University of Havana, Cuba c Superconductivity Laboratory, University of Havana, 10400 Havana, Cuba Taking into account the antacid properties of a purified natural clinoptilolite, NZ, we have examined its effects on aspirin (ASA) in an aqueous medium. We have studied by UV spectroscopy the ASA in solution before and after the addition of NZ. Our results suggest that the concentration of ASA is only affected by the interaction at high pH values (pH=8), at which the ASA also starts to decompose. These results match the IR spectroscopy studies of the incorporation of ASA to NZ. We also exchanged NZ with Ca, Cu and Na ions, and studied the interaction of the modified zeolites with ASA. While no ASA was detected in the zeolite in the first two cases at any pH value, the third one showed some incorporation for all the pH values.
32-P-08 - Channel model for the theoretical study of aspirin adsorption on clinoptilolite. W a t e r influence A. Lain and A. Rivera
Zeolites Engineering Laboratory, University of Havana, anabel@laeJf oc.uh.cu, Cuba A new zeolite model, that features the a and c channels of clinoptilolite has been used to study the possible interactions of aspirin-water-zeolite, in order to know the behavior of the drug in a more complex system and the influence of water present in the zeolite channel. The calculations have been performed using the AM1 semi-empirical method and acid and sodic clinoptilolite models. The results showed that the adsorption entalphy of aspirin in the acid structure is in the same order than that obtained for the sodic structure, although the nature of the interaction is different in each structure. The ester and aromatic groups were preferentially oriented to the model. In any case the chemical stability of aspirin is affected by the presence of water molecules in the system.
374
32-P-09 - In vitro and in vivo effect of natural clinoptilolite on m a l i g n a n t tumors M. Poljak Blazi, M. Katic, M. Kralj, N. Zarkovic, T. Marotti, B. Bosnjak, V. Sverko, T. Balog and K. Pavelic Division of Molecular Medicine, Rudjer Boskovic Institute, pavelic(~rud/er.irb.hr, Croatia Many biochemical processes are closely related to ion exchange, adsorption and catalysis. Zeolites reversibly bind small molecules such as oxygen or nitric oxide, they possess size and shape selectivity, the possibility of metalloenzyme mimicry, and immunomodulatory activity. These properties make them interesting for pharmaceutical industry and medicine. In vitro experiments showed inhibition of tumour cell proliferation as well as MZ to be the possible scavenger of HNE. After i.p. application of MZ, the number of peritoneal macrophages was increased as well as their production of oxide anion. NO generation was totally abolished. At the same time translocation of p65 subunit of NF~:B in spleen cells was observed. Thus, here we report anticancer effect of MZ in vitro and immunostimulatory effect in vivo.
32-P-10 - Effects of natural c l i n o p t i l o l i t e - rich tuff and sodium bicarbonate on milk yield, milk composition and blood profile in Holstein cows A. Nikkhah, A.R. Safamehr and M. Moradi- Shahrbabak Department of Animal Science, Faculty of Agriculture, Tehran University, Tehran, Iran An experiment was conducted to evaluate the effects of different levels of clinoptilolite- rich tuff (CP) and sodium - bicarbonate (SB) on milk yield and its components in Holstein cows. A balanced change - over design with 4 rations, 4 periods (28 days and 4 cows per ration) was employed. Ingredients of the control ration (1) were alfalfa hay (17.1%), corn silage (16.2%) and concentrate (66.7%) on dry matter basis. Experimental rations contained, 1% SB (2) : 0.5% SB + 3% CP (3) and 6% CP (4), respectively. The actual means of daily milk yield of the cows that received rations 1,2,3 and 4 were 23.53, 24.2, 25.24, 25.45 kg/d and milk fat 3.18, 3.39, 3.3 and 3.44%, respectively. The average dry matter intake per kg fat corrected milk (4%fat) for rations 1-4 were, 0.9, 0.95, 0.96 and 0.95, respectively.
32-P-11 - Effect of natural clinoptillolite-rich tuff on the p e r f o r m a n c e of V a r a m i n i male lambs A. Nikkhah, A. Babapoor and M. Moradi- Shahrbabak Department of Animal Science, Faculty of Agriculture, Tehran University, Tehran, Iran In order to determine the effects of different levels of clinoptilolite-rich tuff (CP) on performance of fat tail Varamini male four rations containing 0 (control), 2, 4 and 6% CP which were named 1,2,3 and 4, were prepared, respectively. The rations were fed to four groups of the lamb (12 lambs/group) individually for 100 days. Feed intake, average daily gain (ADG), feed conversion rate (FCR), carcass dressing percentage and carcass quality were measured. The obtained results were as follows: feed intake for rations were 1.32, 1.34, 1.38 and 1.41 kg DM/day, ADC were 166.0, 177.9, 196.9 and 184.8 g/day and FCR were 8.0, 7.6, 7.1 and 7.76, respectively. Dressing percentage of lamb which were fed ration 3, washighest (53.9vs 52.5, 52.7 and 51.2).
375
32-P-12 - Ciinoptilolite and the possibilities for its application in medicine N. Izmirova (a), B. Aleksiev (b), E. Djourova (b), P. Blagoeva (d), Z. Gendjev (d), Tz. Mircheva (d), D. Pressiyanov (c), L. Miner (c), T. Bozhkova (c), P. Uzunov (c), I. Tomova (e), M. Baeva (f), A. Boyanova (f), T. Todorov (g) and R. Petrova (g)
a Sofia University, Faculty of Chemistry; b Faculty of Geology and Geography," c Faculty of Physics, d National Oncological Center," e Sofia Sanitary Inspection,"f BAS Solid Body's Physics Institute, g BAS Applied Mineralogy Inst. Central Mineralogy & Crystallography, Laboratory, Sofia, Bulgaria. Part I. Clinoptilolite (Cpt) is widespread in the NE part of the Rhodopes mountains in Bulgaria. In respect to the possibilities of use of Bulgarian clinoptilolite in medicine, its toxic, genotoxic and carcinogenic effects on laboratory animals, were studied. In the same relation, the natural radioactivity of Cpt, of the animals' food, containing Cpt and of the animals' faeces, was measured. The contents of 226Ra in drinking water, percolating through Cpt rocks and the concentration of 222Rn in Cpt-built houses were also measured. Part II. Products of biocrystallization in human urine dry residue after Cpt application per os were observed too.
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377
AUTHOR INDEX
A Abasov, S.I. 25-P- 15 26-P-20 Abbasova, G.G. 25-P- 15 Abd EI-Hady, H.M. 3 l-P-09 Abe, Y. 24-0-02 Aboukais, A. 14-P- 15 30-P-26 Aboul-Gheit, A.K. 30-P-20 Abraham, A. 13-P-23 Abramova, A.V. 11-P-23 Abramson, S. 29-0-02 Accardi, R.J. 13-P- 12 Afanassiev, I.S. 11-P-26 Agashe, M.S. 14-P- 12 Agayeva, S.B. 26-P-20 Agger, J.R. 02-0-05 Aguado, J. 24-P-13 ,~,gueda, V.I. 18-P- 11 Aguilar-P, J. 25-P-13 Ahedi, R.K. 25-P-06 Ahmed, S.M. 30-P-20 Ahn, W.S. 01-P-14 02-P-19 23-P-14 29-P-13 Ahn, Y.-S. 29-P-27 Aiello, R. 02-P-29 04-P-17 04-P-18 06-P-28 11-P-27 Aika, K. 30-P-34 Aizawa, T. 26-P-07 Akhalbedashvili, L. 23-P-09 30-P-10 Akiyama, Y. 02-P-25 Akporiaye, D. 03-K-01 Akporiaye, D.E. 03-P- 18 Akramzadeh Ardakani, M. 01-P-08 Alberti, A. 01-K-01 Aleksiev, B. 32-P- 12 Aliyev, A.M. 27-P-08 Aliyeva, S.G. 3 I-P-07 Ali-zade, G.A. 27-P-08 AI-Khowaiter, S. 06-P-21 AI-Megren, H. 06-P-21 Altshuler, E. 32-P-07 Alvarez, A.M. 14-P- 14 24-P- 11 Amokrane, S. 23-P-07 Amoureux, J.P. 13-P-2/3 Ananias, D. 0 5 - P - ! ~ Anderson, M. 04-0-05 Anderson, M.W. 02-0-05 13-P-16 21-P-07 27-P-15 Andrade, H.M.C. 30-P-13 Andreev, V.V. 28-P-12 Andr6s, J.M. 18-P- 10 Andrews, R.D. 31-O-02 /
Anfilov, B.G. 01-P-12 Angelescu, E. 24-P-29 Annagiyev, M.Kh. 3 l-P-07 Anpo, M. 30-K-01 14-P-20 14-P-35 15-P-07 15-P-08 28-P-07 30-P-16 30-P-24 Antoni, T. 02-P-24 Antoshin, G.V. 10-P-05 Antunes, A.P. 30-P-23 Anunziata, O.A. 04-P-07 06-P-08 14-P-08 Aoyagi, J. 18-P- 12 Arabindoo, B. 25-0-02 Arafat, A. 02-P-38 Aranzabal, A. 30-P-I 8 Arcon, I. 14-P- 13 Arends, I.W.C.E. 30-0-02 Ariyuki, M. 28-P-07 Armaroli, T. 13-P-25 Armbruster, T. PL-2 Arnold, A.B.J. 29-P-22 Arnold, U. 27-P-06 Asaftei, I. 24-P-30 Asafiei, S. 04-P-09 Atal'yan, O.K. 10-P-05 Attia, A. 22-P- 13 Attou, M. 04-P-09 Aubry, J.-M. 27-P-11 Auerbach, S.M. 16-0-04 Auroux, A. 13-P-07 Avalos, M. 1 l-P-20 Avalos-Borja, M. 0 I-P- 15 Avgouropoulos, G. 29-P-14 Avil, P. 30-P-22 Ayupov, A.B. 13-P-09 Azuma, K. 11-P- 10 Azzouz, A. 04-P-09
B B.Nagy, J.
02-P-29 04-0-03 04-P-14 04-P-I 6 04-P- 17 04-P-I 8 11-P-27 29-P-18 29-P-31 30-P-19 Bahlala, M. 26-P- 15 Baba, T. 24-0-02 Babapoor, A. 32-P-11 Babonneau, F. 07-0-02 Baek, S.-W. 24-P-26 Baerlocher, C. 09-P-14 09-P-11 Baerns, M. 12-P-15 30-P-33 Baetens, D. 04-P-11 Baeva, M. 32-P-12
378
Baggio-Saitovich, E. 14-P-28 Bai, N. 07-P-07 Bakakin, V.V. 0 l-P- 11 Balmer, W. 23-P-06 Balog, T. 32-P-09 Bandyopadhyay, R. 03-P- 10 Bao, X. 30-P-28 B~ir~iny, S. 3 I-P-05 Barbosa, L.V. 24-P-17 Barker, C.M. 15-P- 18 Barnes, P. 01-O-03 Barrault, J. 07-P- 16 Barroudi, M. 06-P- 15 Barsnick, U. 23-P-27 Barth, J.-O. 10-0-02 Basaldella, E I. 20-P-14 20-P-13 Basler, W.D. 11-P-23 Bataille, T. 17-P-09 Batamack, P. 13-P- 13 Batista, M.S. 14-P-28 27-P-12 Battiston, A.A. 12-O-02 Bauer, F. 28-P-06 Bazzana, S. 03-P-13 Beale, A. 14-P-39 Beck, L.W. 03-0-04 Bedard R.L. 05-P-16 Bedekar, A.V. 24-0-04 Bedelean, H. 22-P- 16 Bedelean, I. 22-P- 16 Behrens, P. 02-P-41 06-P-25 10-O-03 Bein, T. 03-P-12 I1-P-15 20-0-04 22-P-11 22-P-14 Belanova, E.P. 10-P-05 Bell, R.G. 13-P-16 16-P-13 16-P-14 Bellat, J.P. 17-O-02 17-P-I 1 Bellussi, G. 25-0-03 29-O-01 Bem, D. 03-K-01 03-P-I 8 05-P-16 Ben T~arit, Y. 10-P-08 13-P-05 Benazzi, E. 26-P-11 Benco, L. 15-0-02 15-P-12 Benetis, N.P. 14-P-09 Bengoa, J.F. 14-P- 14 20-P- 13 24-P- 11 Bengueddach, A. 03-P-19 17-P-14 Benmohammadi, I~. 21-O-04 Bergmann, M. 14-P-31 Bernaue, B. 14-P-38 Berndt, H. 10-O-01 30-P-15 Berthomieu, D. 15-P-23 Bertrand, O. 17-0-02 17-P-11 Bessho, H. 15-P-07 Beta, I.A. 12-P-08 Bevilacqua, M. 13-P-25 Beyer, H.K. 07-0-03 10-P-06 Bharathi, P. 15-P-09 Bichara, C. 15-P- 26 Bilba, N. 24-P-30 04-P-09 Binet, C. 27-0-05
Birjega, R. 07-P-14 Bischof, C. 26-P-18 Bitter, J.H. 12-O-02 19-P-08 Blagoeva, P. 32-P-12 Blanc, A.C. 29-0-02 29-P-10 29-P-31 Blanco, C. 03-P-06 Blanco, M.N. 23-P-19 Blasco, T. 12-P-12 29-P-23 Bliek, A. 28-P-14 Bobonich, F. 31-P-05 Boenneman, H. 29-P-22 Bogdanchikova, N. 0 l-P- 15 1l-P-20 B6hlig, H. 12-P-08 B6hlmann, W. 06-P-I 7 14-P-07 BOhringer, W. 11-O-02 28-P-15 Boissi6re, C. 08-O-01 08-P-05 Bonardet, J.-L. 19-K-01 19-P-09 Bonelli, B. 22-P-21 BOngyikand, E. 27-P-10 Bonino, F. 14-P-34 Bonneviot, L. 06-0-03 Bonnin, D. 11-O-01 Bordiga, S. 14-P-34 15-O-05 24-P-15 Borello, L. 13-0-04 Borges, C. 02-P-33 Boron, S. 22-P-20 Borovkov, V.Y. 12-O-04 Bosnjak, B. 32-P-09 Botavina, M.A. 30-P-09 B6ttcher, R. 14-P-07 Boutin, A. 16-0-03 Bouvier, F. 17-P-I 1 Boyanova, A. 32-P- 12 Bozhkova, T. 32-P- 12 Bradley, S.A. 26-P-06 Brand~io, P. 04-0-05 27-P-15 Brandmair, M. 30-P-30 Braos-Garcia, P. 23-P-28 Bratu, C. 03-P-18 Br/iuer, P. 28-O-01 Brehm, M. 21-O-03 Br6mard, C. 14-P-18 14-P-24 Bricker, M. 03-K-01 Brieler, F. 21-O-03 Broach, R.W. 05-P-16 Broclawik, E. 15-P- 13 Brodyn, M. 22-P-18 22-P-20 Broersma, A. 19-P-08 Bronic, J. 02-P-24 02-P-29 Brtihwiler, D. 14-0-04 Brunel, D. 29-0-02 29-P- 10 29-P-31 Buchholz, A. 14-P- 17 Budneva, A.A. 11-P-26 Buhl, J.C. 02-P-07 13-P-15 Buijsse, E.J.W. 20-P-18 Bulow, M. 12-O-04 03-0-05 18-O-03 Burtica, G. 01-P-09 06-P-22
379
Busca, G. 13-P-25 Buschmann, V. 02-0-01 02-P-06 Busco, C. 15-0-05 Bussaia, C. 15-P-28 Bustamante, F. 30-P-22 Buttefey, S. 16-0-03 Buttersack, C. 18-0-02 BtiyfikgtlngOr, H. 3 I-P- 14 Byggningsbacka, R. 24-P- 16
C Caceres, C. 23-P- 19 Cadoni, M. 30-P-31 Cagnoli, M.V. 14-P- 14 24-P- 11 Cai, T.-X. 25-P-09 Cairon, O. 14-P-23 Calb, I. 01-P-09 Calder6n, M. 26-P-12 Callanan, L.H. 11-P-25 Calleja, G. 07-P-12 Calzaferri, G. 14-O-04 Camblor, M.A. 05-P-07 13-O-01 Campelo, J.M. 25-P-11 Cao, G. 1 l-P- 19 Cao, J.M. 22-P-08 Cappelletti, P. 01-O-02 Caputo, D. 01-O-05 3 l-P-13 Carati, A. 14-P-30 Cardoso, D. 14-P-36 Carlos, L.D. 05-P-12 Carlsson, A. 03-0-02 Carlsson, K.A. 02-P- 16 Carluccio, L. 29-0-01 Carpentier, J. 30-P-26 Cassiers, K. 06-P-11 Castagnola, N. 28-0-03 Castanheiro, J.E. 23-P- 19 Catlow, C.R.A. 01-O-03 14-P-39 15-P-18 16-0-02 Caullet, P. 09-O-01 25-0-04 Caumo, L. 24-P-17 t~ejka J. 06-P-20 13-0-02 13-P-19 14-P-21 14-P-22 25-P-10 Centi, G. 31-O-03 Cerjan-Stefanovic, 3 l-P-11 0 l-P-17 Cerri, G. 01-O-02 Cesteros, Y. 23-P-16 Chai, H.S. 27-P- 14 Chanda, B. 24-0-04 Chandwadkar, A.J. 07-P-20 Chang, J.-S. 03-P-15 22-0-03 Chang, S.H. 02-P-19 Chao, K.J. 07-P-13 20-0-05 29-P-25
Chao, M.-C. 08-P-07 Chaplin, M.F 16-P- 10 Charkviani, M.K. 23-P-26 Chatterjee, A. 15-P-06 Chatterjee, M. 07-P-06 Che, M. 14-P-20 14-P-35 Che, S. 06-P-18 14-P-26 Cheetham, A.K. 05-0-05 22-0-03 Chelaru, C. 25-0-04 Chen, C.Y. 02-0-05 II-P-16 17-P-07 26-0-05 Chen, J. 05-0-02 Chen, J.G. 26-0-04 Chen, J.-S. 05-P-11 l l - P - l l 1 l-P- 12 2 I-P-08 Chen, L. 21-O-03 Chen, L.R. 1 I-P-08 Chen, M. 05-P-06 Chen, Q. 12-P-05 24-P-06 Chen, T.-H. 13-P-18 14-P-10 14-P-11 Chen, W. 05-P-I 1 Chen, We. 12-P-05 24-P-06 Chen, X. 24-P-12 Chen, Y. 29-P-08 Chen, Y.B. 12-P- 11 Chen, Yo. 27-0-02 Cheng, M. 30-P-28 Cheng, W. 2 l-P-11 Cheng, X. 22-0-04 Cheng, Z.L. 28-0-02 Cheralathan, K.K. 25-0-02 Chevreau, T. 14-P-23 27-0-05 Chezeau, J.M. 09-P-I 1 Chia, L.S. 05-P-20 Chihara, K. 18-P- 15 Chiranjeevi, T. 26-P-17 Chiu, Y.W. 20-0-05 Choi, E.Y. 09-P-06 Choi, K. 03-P- 12 Choi, S.-D. 23-P-10 Choi, Y. 23-0-04 Cholley, T. 24-0-03 Choung, S.J. 30-P-32 Christaki, E. 32-P-06 Chuichay, P. 15-0-04 Chun, Y. ll-P-09 30-P-08 Chun, Y.S. 20-0-01 Chung, Y.M. 29-P-13 Ciambelli, P. 16-P-20 30-P-31 30-P-35 Clark, L.A. 15-P-19 16-O-05 Clerici, M.G. 14-P-30 Clet, G. 20-0-02 Climent, M.J. 23-P-21 23-P-22 Colella, A. 01-O-05 Colella, C. 01-O-05 31-P-I 3 Colic, M. 32-O-01 Collart, O. 29-0-04 Collignon, F. 28-P-11
380
Coloma, F. 29-P- 15 Coluccia, S. 14-O-05 29-P-30 30-P-31 Concepcion Rosabal, B. 01-P-15 Concetta Gaudino, M. 30-P-35 Conradsson, T. 09-0-03 09-P-12 Conz, V. 24-P- 17 Cook, B.R. 26-0-04 Cool, P. 06-P- 15 07-P- 18 Coq, B. 15-P-23 30-P-06 Corma, A. 11-P-29 23-K-01 25-P-13 23-P-21 23-P-22 24-P-20 29-P-30 32-0-05 Cornet, D. 26-P-15 27-0-05 Corr~a, R.J. 24-P- 19 Costa, C. 15-P- 16 Coulomb, J-P. 17-O-02 17-O-03 17-P-05 Cox, P.A. 05-0-03 Crea, F. 04-P- 17 Creaser, D. 02-0-03 20-P-09 Crow, P. 2 l-P-07 Cruciani, G. 01-K-01 09-P-13 Cui, W. 24-P-28 Cundy, C.S. 02-0-02 02-P-08 21-P-07
D d'Espinose de la Caillerie, J.-B. 08-0-04 da Cruz, R.S. 27-P-06 Daage, M. 26-0-04 Dadachov, M.S. 09-0-03 09-P-12 Dadashev, B.A. 26-P-20 Daelen, G. 11-P-27 Dahl, I. 03-K-01 03-P-18 Dahlhoff, G. 23-P-27 Dai, Z. 22-0-02 Dakovic, A. 32-0-04 Dalea, V. 22-P- 10 Dalloro, L. 15-0-05 Dalmon, J.-A. 14-P-38 Damin, A. 14-P-34 Damodaran, K. 13-P-20 Dams, M. 23-0-02 Dapaah, J.K.A. 26-P-07 Darkrim, F. 17-P- 10 D,'iscalescu C. 29-P-21 Datka, J. 13-P-17 15-P-13 Davidov~i, M. 14-0-03 Davidson, A. 08-0-03 Davis, M.E. PL-3 02-P-27 02-P-28 De bruyn, M. 23-P-33 de Castro B. 2 l-P- 13 de Gauw, F.J.M.M. 28-0-05 de Gennaro, B. 01-O-05 3 l-P- 13 de Gennaro, M. 01-O-02 01-O-05 de Jong, A.M. 19-P- 10
de Jong, K.P. 14-O-01 19-P-08 de los Reyes, J.A. 25-P- 13 De Luca, P. 04-P-I 6 de M6norval, L.-C. 14-P-37 23-P-13 de Souza, M.O. 24-P- 17 de Souza, R.F. 24-P- 17 De Vos, D.E. 23-0-02 23-P-33 27-P-11 deCastro, C. 29-0-03 Decyk, P. 07-0-04 27-P-09 D~,de~,ek J. 13-0-02 13-P- 19 14-P-21 Deere, J. 23-P- 17 Delabie, A. 15-P- 11 Delahay, G. 15-P-23 30-P-06 Dellarocca, V. 29-P-30 Delmotte, L. 09-O-01 Demuth, T. 15-0-02 15-P- 12 Deng, F. 08-P-08 Dereppe, J.-M. 19-K-01 Derevyankin, A.Yu. 08-P-14 Derewifiski M. 04-0-04 24-P-10 Derouault, A. 07-P-I 6 Derriche, Z. 17-P- 14 Desplantier-Giscard, D. 06-P-27 Di Benedetto, A. 16-P-20 Di Renzo, F. 03-P-I 9 04-0-01 06-P-27 06-P-28 13-P-I 1 29-0-02 29-0-04 Diaz, I. 07-P- 17 08-P-10 Diaz, L. 23-P-28 Diaz-Cabaflas, M.J. 24-P-20 Dimitrov, M. 07-P- 19 Ding, D. 16-P-07 Ding, H. 22-P-09 28-0-02 Djourova, E. 01-P-I 0 32-P-12 DObler, J. 12-O-03 12-P-08 Dolinsky, S.E. 24-P-09 Domen, K. 07-P-I 5 12-P-06 Domiciano Fernandes, L. 06-P-24 D6mine, M.E. 11-P-29 Dominguez, J.M. 08-P-09 Dondur, V. 32-0-04 Dong, B. 14-P-25 Dong, J. 1 l-P-13 2 l-P-09 Dong, M. 04-P-I 5 14-P-32 dos Santos, J.H.Z. 24-P-17 Dou, T. 06-P- 10 Drerman, J. 07-0-05 Drijkoningen, L. 23-0-02 Drozdov~, L. 11-O-05 Du, Z. 16-P-10 Duarte, M.T. 02-P-33 Dubsk~, J. 24-P-10 Duc6r6, J-M. 15-P-23 Dudarev, S.V. 02-P-20 02-P-31 Duersch, B.S. 03-0-04 Dufau, N. 17-0-03 Dumitriu, E. 25-0-04 Dumrui, S. 03-P- 13
381
Duncan, W.L. 19-0-03 Dunne, L.J. 16-P- 10 Dutta, P.K. 28-0-03 Dwyer, J. 14-P- 13 Dzwigaj, S. 14-P-35
E Ebigase, T. 24-P-25 Ebina, T. 07-P-06 Echavarria, A. 09-P-07 Echevsky, G.V. 02-P-20 13-P-09 Eckelt, R. 30-0-04 Eckhard, J.-F. 23-P- 13 Edrissi, M. 02-P-09 Ei4, M. 19-P-06 Eickelberg, W. 23-P-27 Eimer, G.A. 06-P-08 Elder, S.H. 22-P-13 Ellis, E.S. 26-0-04 Elomari, S.A. 03-0-03 Elstner, M. 15-P-25 Erdem-~;enatalar, A. 19-0-05 20-P- 15 Erdmann, K. 24-P-22 Ernst, S. 04-0-02 14-P-21 28-P-10 29-P-19 Escalona Platero, E. 12-P- 13 Escola, J.M. 24-P- 13 Essayem, N. 13-P-05 Eswaramoorthi, I. 29-P-24 Evmiridis, N.P. 29-P-06
F Fajula, F.
03-P-19 06-P-27 06-P-28 1 l-P-06 13-P-11 23-P-13 24-0-03 29-0-02 29-0-04 29-P-31 Falamaki, C. 02-P-09 Fan, B. 02-P-14 07-P-10 21-P-11 Fan, J. 08-P-11 Fan, W. 04-P-13 07-P-10 F~isi, A. 23-P- 15 Fatullayeva, S.S. 27-P-08 Fechete, I. 25-0-04 Fejes, P. 04-P- 17 04-P-I 8 Fenelonov, V.B. 08-P- 14 Feng, S. 22-0-02 Fenoglio, I. 32-0-02 Ferchiche, S. 02-P- 17 Ferey, G. 22-0-03 05-P-19 16-P-15 Fermann, J.T. 16-0-04 Fernandez, C. 09-P-11 13-O-03 13-P-24
Ferraris, G. 30-P- 14 30-P-21 Ferreira, A. 05-P-12 Ferreira, P. 05-P-12 Ferreira, R. 2 I-P-I 3 Ferrer, P. 18-P- 10 Fiermans, L. 27-P- 11 Fierro, G. 30-P- 14 Figueiredo, J.L. 21 -P- 13 Fild, C. 13-0-01 Filip, D. 06-P-22 Finiels, A. 23-P-06 24-0-03 Fisher, K.J. 14-P-29 Fitch, F.R. 03-0-05 FjelMig, H. 05-0-05 Flego, C. 14-P-30 Fleitas, A. 32-0-03 Floquet, N. 17-O-02 17-0-03 17-P-05 Flora, L. 22-P-21 Florou-Paneri, P. 32-P-06 Fois, G.A. 15-0-05 Fomin, A.S. 10-P-05 Fonseca, A. 04-0-03 04-P-14 04-P-16 04-P-I 8 11-P-27 29-P-18 Foran, P. 21-P-07 Fom4s, V. 23-K-01 23-P-21 Forrest, J.O. 02-0-02 02-P-08 Forster, P.M. 22-0-03 Fortomaris, P. 32-P-06 Foster, M.D. 16-P- 13 Frache, A. 30-P-31 Fraissard, J. 06-P-16 11-O-01 13-P-13 14-P-27 19-K-01 19-P-09 Franqois, V. 17-P- 11 Freire, C. 2 I-P-13 Freude, D. 14-0-02 Freyer, A. 28-P-06 Fricke, R. 13-P-21 2 l-P- 14 30-0-04 Fripiat, J.J. 07-P-11 Fritzsche, S. 16-P- 18 FrOba, M. 07-P-19 17-P-12 Fromentin, E. 25-P-08 Frontera, P. 02-P-29 Frunza, L. 03-P-16 2 l-P- 14 Frunza, S. 21-P-14 Fu, J. 26-O-01 Fu, Y. 05-0-02 Fu, Z. 29-P-08 Fubini, B. 32-0-02 Fuchs, A.H. 16-0-03 Fukuoka, A. 22-0-05 Fukushima, T. 11 -P- 10 Fukushima, Y. 02-P-27 17-O-04 22-0-05 Furukawa, K. 1 I-P- 17 Furusawa, T. 30-P-34
382
G Gabdrakipov, A.V. 15-P- 14 Gabdrakipov, V.Z. 15-P- 14 Gabelica, Z. 02-P-33 04-0-01 07-P-16 14-P-40 24-0-05 Galarneau, A. 06-P-27 29-0-02 29-0-04 Gale, J.D. 16-P- 15 Galkina, N.K. 0 l-P- 12 22-P- 12 Gallegos, N.G. 14-P-14 24-P-11 Galli, E. 01 -K-01 Galli, P. 30-P-21 Galperin, L.B. 26-P-06 Gammon, D.W. 27-P-17 Ganapathy, S. 02-P-40 13-P-20 13-P-23 Ganea, R. 07-P- 14 Ganschow, M. 21-O-02 Gao, B. 09-P0-8 Gao, F. 03-P-08 09-P0-8 21-O-05 Gao, X. 24-P-28 Gao, Y.R. 28-0-02 Gao, Z. 21-P-06 Gaona, J.A. 11-P-29 Garagorri, E. 24-P-13 Garcia, A. 25-P-11 Garcia, R. 05-0-03 Garcia, H. 23-P-21 Garcia-Serrano, L.A. 29-P-23 Garrone, E. 04-0-01 13-0-04 14-P-40 22-P-21 29-P-31 Gautier, S. 13-0-03 Gavlina, O.T. 1 I-P- 18 Gedanken, A. 06-P- 14 Gedeon, A. 08-P-14 08-0-04 13-P-I 3 Geidel, E. 12-O-03 12-P-08 Geier, O. 19-0-04 Gendjev, Z. 32-P-12 Gener, I. 14-P-I 8 14-P-24 Geobaldo, F. 04-O-01 13-O-04 14-P-40 Georgescu, V. 22-P-10 Ghanbari-Siahkali, A. 14-P-13 Ghorbel, A. 10-P-08 Ghrir, A.M. 31-O-01 Giamello, E. 14-0-05 Giannetto, G. 28-P- 13 Gianotti, E. 14-0-05 Gicquel, A. 17-P- 10 Gier, T.E. 05-0-05 Gies, H. 09-0-05 Gijzeman, O.L.J. 19-P-08 GiI, B. 13-P-17 15-P-13 Gillespie, R. 03-K-01 Gilson, J.-P. 12-O-01 27-0-05 Giordano, G. 04-0-03 04-P-14 29-P-05 Girard, S. 05-P-19 07-P-21 16-P-15
Gisselquist, J. 05-P- 16 Gl~tser, R. 23-0-03 Gobin, K. 30-P- 17 Goddard III, W.A. 16-P-09 Goddeeris, M. 23-P-20 Goh, N.K. 05-P-20 Goldwasser, M.R. 03-P-11 Goletto, V. 07-0-02 G6mez, J.M. 18-P- 11 G6mt~ry, A. 23-P-15 Gon~alves, F. 27-P- 15 Gong, Y. 08-P-08 Gonzalez, G. 14-P- 19 Gonz~lez, F. 03-P-06 Gonz~ilez, L. 28-P-13 Gonz~lez-Pefia, V. 06-P-23 Gonz~ilez-Velasco, J.R. 30-P- 18 Goossens, A.M. 02-P-06 Gopal, S. 26-P-16 Gopinath, C.S. 07-P-20 Gora, L. 20-0-02 20-P-18 G6ra-Marek, K. 13-P- 17 Gorbatkina, I.E. 26-P-23 Gorshkov, V.I. 1 l-P- 18 Goryainov, S.V. 16-P- 19 Goto, Ya. 02-P-27 17-0-04 Goto, Yu. 17-0-04 Gotoh, K. 13-P- 14 Goursot, A. 15-P-23 15-P-24 15-P-25 Graffin, P. 23-P-13 Gray, A.E. 16-P- 11 Green, M.L.H. 06-P-21 Grigoryan, A. 23-P-08 Grigoryan, F. 01-P-16 Grill, W. 02-P-37 Grillet, Y. 17-P-05 Grimm, A. 31-O-04 Grinev, V.G. 22-P-15 Grobet, P. 13-P-18 14-P-10 14-P-11 23-P-33 27-P-11 Groen, J.C. 17-P-08 Groothaert, M.H. 15-P- 11 Grtinert, W. 10-O-01 30-P-15 30-P-27 Grianwald, A. 3 l-P-09 Gryshchouk, G.V. 3 l-P-08 Gualtieri, A.F. 01-O-04 Guan, N. 12-P-15 30-P-33 Guillemot, D. 11-O-01 Guimon, C. 25-0-04 Guisnet, M. 25-P-08 30-0-05 30-P-23 Guo, C.J. 18-0-03 Guo, H.C. 28-P-08 Guo, J. 29-P-08 Guo, S. 20-P-07 Guo, W. 02-P-35 Guo, X. 27-0-02 24-P-14 Guo, Y. 1l-P-11
383
Guo, G.-Q. 03-P-09 18-P-08 Gupta, A. 16-0-05 Gupta, R. 13-P-20 Guth, J.-L. 18-P-06 Guti6rrez Alejandre, A. 13-P-25 Guti6rrez-Ortiz, J.I. 30-P- 18 Gutjahr, M. 14-P-07
H Ha, B.-H. 02-P- 10 Ha, K. 20-O-01 Haberlandt, R. " 15-P-28 16-P- 18 Haddad, E. 08-P-14 Hafner, J. 15-O-02 15-O-03 15-P-12 15-P-20 Hajnal, Z. 15-P-25 Hal,'tsz, J. 29-P- 18 Hailer, G.L. 06-P- 12 23-P-16 Halsall-Whitney, H. 18-0-01 Hamada, H. 02-P-26 02-P-30 Hamdan, H. 25-P-12 Hambartsumyan, A. 0 I-P- 16 Hamidi, F. 03-P- 19 Han, M. 1l-P-21 Han, M.-H. 29-P-27 Han, Y. 05-P-09 06-P-07 Han, Y.W. 09-P-06 Hanaoka, T. 02-P-30 28-P-09 Hancs6k, J. 26-P- 19 Handan Tezel, F. 18-0-01 Haneda, M. 04-P-06 Hanif, N. 02-0-05 04-0-05 Hanika, J. 25-P-10 Hannongbuai, S. 15-P-28 Hannus, I. 30-P- 19 Hantzer, S. 26-0-04 Hao, J. 1 l-P- 13 Haouas, M. 11-P-28 13-P-22 29-P-28 Harlick, P.J.E. 18-0-01 Haroyan, H. 0 l-P- 16 Harrison, W.T.A. 05-0-01 Hartl, M. 10-0-03 Hartmann, M. 04-0-02 26-P-18 28-P-10 29-P-19 Hashimoto, K. 17-P- 13 Hattori, T. 24-P-25 30-0-03 Hayashi, H. 07-P-06 Hayashi, S. 1 l-P-07 13-P-06 He, H. 16-P-16 He, M.-Y. 02-P-34 26-O-01 He, Y.J. 12-P- 11 He, B. 30-P-24 Hecht, T. 29-P-19 Hedlund, J. 02-P-12 20-P-08 20-P-09 20-P-10
Heimbrodt, W. 21-O-03 Heine, T. 15-P-25 Heinrich, F. 30-P-27 Henriques, C. 02-P-33 Henriques, C.A. 24-0-05 Heo, N.H. 09-P-10 Herman, S. 0 l-P-09 Hernadi, K. 27-P-10 Hernfindez, I. 25-P-13 Hem~ndez, J.C. 28-P- 13 Hern~indez, S. 18-P- 10 Herrier, G. 08-0-02 Herrmann, R. 02-P-37 Heydenrych, H. 11-P-24 Hidajat, K. 06-P-26 Higashimoto, S. 14-P-20 28-P-07 30-K-01 Hilbrandt, N. 03-P- 12 Hoang, D.L. 13-P-21 Ho~evar, S. 19-P-06 Hodnett, B.K. 23-P-17 HC~lderich, W.F. 23-P-27 25-P-14 29-P-22 29-0-03 Hol16, A. 26-P-19 Holmes, S.M. 21-P-07 Holmgren, J. 03-K-01 Holmqvist, A. 13-P-05 Honda, T. 02-P-27 Hong, S.B. 05-P-07 02-P-10 Hoogesteger, A.W. 03-P-17 Horiuchi, T. 12-P- 11 Horniakov~i, J. 25-P-07 29-P-11 Houssin, C.J.Y. 02-0-01 Hou~vieka, J. 03-0-02 26-0-02 Hovnanian, N. 08-P-05 Howe, R.F. 14-P-29 Hrenovic, J. 31 -P- 14 Hronec, M. 25-P-07 Huang, L. 08-P-13 20-P-I 1 22-0-04 Huang, W. 06-P-14 Huang, W.Y. 18-P-07 Huang, Y. 14-P- 16 HUbner, G. 12-P-09 Hudec, P. 24-P-10 29-P-26 Hudson, C.W. 26-0-04 Hufnagel, V.J. 02-P-41 Hugeunard, C. 05-P-19 09-0-02 Hulea, T. 25-0-04 Hulea, V. 25-0-04 29-0-02 Hunger, B. 12-O-03 12-P-08 Hunger, M. 14-P-17 23-P-12 23-P-23 Hutschka, F. 15-O-02 15-O-03 15-P-12 15-P-20 15-P-22 Hwang, J.S. 27-P- 14
384
Iborra, S. 23-P-21 Ibrahim, K.M. 31-O-01 Ichikawa, M. 13-P- 14 22-0-05 Igarashi, N. 17-P- 13 Ihm, S.-K. 24-P-26 26-P-21 ljiri, H. 1 l-P- 17 Ikeda, R. 13-P- 14 Ikeda, T. 02-P-25 21-P-18 22-P-17 Iiiev, Tz. 01 -P- 13 Illgen, U. 30-P-33 Ilyin, V. 3 l-P-05 Imada, Y. 17-O-04 28-P-09 Imamura, M. 04-P-06 lmbert, F.E. 28-P- 13 Imp6ror, M. 07-0-02 08-0-03 Inagaki, S. 03-P-14 22-0-05 Inaki, Y. 24-P-25 Inversi, M. 30-P- 14 Ioannides, T. 29-P- 14 Iofcea, Gh. 24-P-30 lojoiu, E.E. 30-P- 12 lone, K.G. 02-P-23 Iovi, A. 01-P-09 lshimaru, K. 14-P-06 lshimaru, S. 13-P- 14 ltabashi, K. 01-P-07 lto, S. 1 I-P-07 30-P-I 1 Ivanov, V.A. 11 -P- 18 lvanova, I.I. 1 l-P-06 23-P-12 25-0-05 lvanova, R. 0 l-P- 13 Iwasaki, T. 07-P-06 15-P-06 Izard, V. 29-0-02 Izmirova, N. 32-P- 12 Izuhal, S. 29-P-29 Izumi J. 18-P- 12
Jacob, N.E. 14-P- 12 Jacobs, P.A. 02-0-01 02-0-04 12-P-10 23-002 23-P-20 23-P-33 27-P-11 Jacobsen, C.J.H. 03-0-02 26-0-02 Jfinchen, J. 31-O-04 Janicke, M. 29-P-17 Jankowska, A. 22-P-19 Jansen, J.C. 02-P-38 03-P-17 20-0-02 20-P- 18 Janssen, A.H. 14-0-01 Jentys, A. 11-P-24 26-P-13 27-0-04 30-P-30 Jeong, S. 14-P-29 Ji, S.-F. 06-P-21
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385
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386
Kujawa, J. 27-P-09 Kukovecz, A. 04-P- 18 11-P-27 Kulak, A. 20-0-01 Kuliyev, A.R. 27-P-08 Kuliyev, T.M. 3 l-P-07 Kulkami, S.J. 23-P-24 28-0-04 Kulprathipanja, S. 18-0-05 Kumakiri, I. 20-P- 16 Kumar, N. 23-P-25 24-P-16 Kumar, P. 26-P- 17 Kumar, R. 02-P-40 07-P-23 25-P-17 Kunieda, K. 29-P-29 Kunimori, K. 1 l-P-07 30-P-11 Kurata, Y. 02-P-30 Kuriyavar, S. 10-0-04 Kurpan, E. 02-P- 12 Kustov, A.L. 14-P- 15 Kustov, L.M. 26-0-03 26-P-23 Kuz'ma, Yu.B. 31-P-08 Kuznicki, S. 11-O-04 Kwon, S.P. 02-P- 10
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387
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388
Matiyev, K.I. 27-P-08 Matsukata, M. 03-P-14 07-P-24 1 I-P-30 20-0-03 Matsunaga, I. 03-P- 14 Matsuoka, M.
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N Naccache, C. 10-P-08 Nachtigall, P. 14-0-03 Nachtigallov~t, D. 14-O-03 Nagai, M. 12-P-17 29-P-29 Nagase, T. 07-P-06 Nair, S. 02-P-28 Naitza, S. 01-O-02
389
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O O'Connor, C.T.
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390
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391
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392
Sassoye, C. 05-P-19 Sastre, E. 06-P-23 07-P-I 7 08-P- 10 29-P-23 Sato, M. 16-P- 17 Sato, T. 1 l-P-07 Satsuma, A. 24-P-25 30-0-03 Satyanarayana, C.V. 13-P-20 23-P-31 Sauer, J. 15-0-01 29-P- 17 Sauerbeck, S. 04-0-02 Sautet, P. 15-P- 17 Sawada, H. 24-0-02 Scharf, O. 02-P-37 Scharl, H. 26-P- 10 Scheffler, F. 20-P- 17 Schenk, M. 16-0-01 Schenk, U. 14-P- 17 Schenkel, R. 10-0-02 Schertlen, R. 02-P-37 Schmachtl, M. 02-P-37 Schmidt, C. 10-O-01 30-P-15 Schmidt, I. 03-0-02 26-0-02 Schmidt, W. 02-P-23 10-P-07 29-P-25 Schmitzer, S. 30-P- 12 Schneider, A.M. 02-P-41 Schomburg, C. 22-P-07 Sch6nhals, A. 2 I-P- 14 Schoonheydt, R.A. 03-P- 16 04-P- 11 04-P- 13 12-O-03 15-O-03 15-P- 11 Schreier, E. 30-0-04 Schuchardt, U. 27-P-06 Schulz-Ekloff, G. 21-O-02 22-P-06 22-P-07 Schuring, D. 19-P- 10 Schtiring, A. 16-P- 18 Schtith, F. PL-I 02-P-23 21-O-04 29-P-17 29-P-25 SchUtze, F.-W. 10-O-01 30-P-15 Schwan, P. 28-P- 16 Schwieger, W. 02-P-36 02-P-37 20-P-17 Seelan, S. 14-P- 12 Serf, K. 09-P-06 09-P-10 Seino, A. 26-P-07 Selvam, T. 02-P-36 Seo, G. 23-0-04 23-P-18 25-P-16 Seo, H.K. 30-P-32 Sep61veda-Escribano, A. 29-P-15 Serrano, D.P. 06-P-I 3 07-P- 12 24-P- 13 Serykh, A.I. 12-0-04 Seryotkin, Y.V. 11-P-26 Seshan, K. 30-P-30 30-P-34 Setoyama, N. 17-0-04 Sevcikov~, B. 23-P-25 Sferdjella, S. 21-P-12 21-P-15 Shah, M.J. 11 -P- 19 Shakhtakhtinsky, T.N. 27-P-08 Shan, X. 12-P-15 30-P-33 Shanthi, K. 26-P- 14 Shao, C. 03-P-08 21-O-05 She, L.-Q. 1 l-P-21
Shen, D. 18-O-03 Shen, B. 30-P-07 Shen, J.-P. 25-0-01 Sheptovetzkaya, K.I. 0 l-P- 12 22-P- 12 Sheu, H.-S. 08-P-07 Shi, C. 30-P-28 Shi, Z. 05-0-04 05-P-06 05-P-10 22-0-02 Shichi, A. 30-0-03 Shimidzu, W. 20-P-16 Shimizu, S. 02-P-26 Shin, C.-H. 02-P- 10 Shin, I.S. 07-P-22 Shiotani, M. 14-P-09 Shmakov, A.N. 08-P-14 Shu, X.-T. 02-P-34 30-P-29 Shvets, O. 22-P-18 22-P-20 Sicard, L. 07-P-08 Sidamonidze, Sh. 23-P-09 30-P-10 Sierka, M. 15-0-01 Sierra, L. 18-P-06 Siffert, S. 30-P-26 ,~ilhan M. 14-0-03 Silva, I.F. 23-P-19 Silva, J.M. 21-P-13 30-P-23 Silvestre-Albero, J. 29-P-15 Sim6n Carballo, R. 32-0-03 Simon, A. 09-P-07 11-O-03 Simon, L. 26-P-13 27-0-04 Simperler, A. 13-P- 16 Singh, A.P. 23-P-30 Singurei, G. 22-P- 16 Sivakumar, T. 26-P- 14 Sivasanker, S. 13-P-20 13-P-23 14-P-12 15-P-09 Sj6blom, J. 06-P-16 Slabov~i, M. 06-P-20 Slater, B. 16-0-02 Slawin, A.M.Z. 05-0-03 Slivinsky, Ye.V. 11-P-23 Sloan, J. 06-P-21 Smaihi, M. 02-P- 18 Smie~kov~, A. 24-P- 10 29-P-26 Smimiotis, P.G. 26-P-16 Smimov, A.V. 25-0-05 Smimov, M.B. 16-P- 19 Smit, B. 16-0-01 Snurr, R.Q. 15-P-19 16-O-05 Sobalik, Z. 10-0-04 13-P-19 Sobczak, I. 07-0-04 Sobolev, W. 3 I-P-05 Sohrabi, M. 02-P-09 Solcova, O. 26-P-22 Solovyov, L.A. 08-P-14 Sominski, E. 06-P-14 Son, T.-M. 23-P- 14 Song, C. 25-O-01 Song, L. 19-O-02 28-0-02
393
Song, S.G. 05-P-16 Song, Y. 02-P- 11 Soni, H.S. 07-P-20 Sotelo, J.L. 18-P- 11 Sowade, T. 10-O-01 30-P-I 5 Span6, G. 14-P-34 15-0-05 Spehlmann B. 18-0-05 Spliethof, B. 29-P-22 Spojakina, A.A. 26-P-22 ~poner J.E. 10-O-04 Springuel-Huet, M.-A. 06-P-I 6 14-P-27 19-K-01 19-P-09 Sridevi, U. 23-P-31 Srinivas, D. 07-P-20 14-P-12 Srinivas, N. 28-0-04 Srinivasu, P. 23-P-24 Stach, H. 31-O-04 Stachurska, M. 04-0-04 Stein, B. 1 I-P- 15 Stenzel, C. 02-P-37 Sterte, J. 02-0-03 03-P-07 20-P-08 20-P-09 20-P-10 Stevens, C.L.T. 24-P-21 Stoch, J. 07-0-04 Stock, N. 03-P-12 St0cker, M. 06-P- 16 Stojsic, D. 32-0-04 Storeck, W. 13-P-21 Str6~2yk, M. 22-P- 19 Struzhko, V.L. 30-P-25 Stucky, G.D. 05-0-05 08-P-12 22-P-20 Stuhler, S.L. 02-P-21 Su, B.-L. 08-0-02 29-P-21 Suboti6, B. 02-P-24 02-P-29 02-P-32 32-0-01 Sudarsan Kumar, I. 25-0-02 Sueiras, J.E. 23-P- 16 Sugi, Y. 02-P-27 03-P-10 17-0-04 25-P-06 25-P-16 28-P-09 Sugimoto, N. 22-0-05 Sugimura, T. 28-P-09 Sugioka, M. 26-P-07 Sugiyama, K. 05-P-09 Suh, Y.-W. 23-P- 14 Sumiya, S. 1 l-P- 10 Sun, C. 05-P-17 05-P-18 24-O-01 Sun, J. 27-P-07 Sun, L. 25-0-01 Sun, P. 16-P-07 Sun, W.F. 1 l-P-08 Sun, Y. 29-P-07 Sun, Y.-H. 04-P-15 07-P-09 08-P-08 14-P-25 Sun, Y.-H. 14-P-32 Sun, Y.-J. 03-P-09 Sun, Z.L. I1-P-08 19-O-02 28-0-02 Sundaramurthy, V. 29-P-24 Suo, J. 24-P-12
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394
Tomatis, M. 32-0-02 Tomova, I. 32-P-12 Torales, A. 25-P-13 Torosyan, G. 23-P-08 Torracca, E. 01-O-05 Torres, M.A.M. 14-P-28 Tosheva, L. 03-P-07 Toufar, H. 02-P-37 Toukoniitty, E. 23-P-25 Toulhoat, H. 15-0-02 15-P- 12 Touvelle, M.S. 26-0-04 Traa, Y. 26-P- 10 Trgo, M. 01 -P- 17 Triantafillidis, C.S. 29-P-06 Tripathi, A. 05-0-01 Trombetta, M. 13-P-25 Trong On, D. 06-0-03 Trunschke, A. 12-P- 15 Truong, T.N. 15-0-04 15-P- 10 Tsapatsis, M. 02-P-28 Tserveni-Gousi, A. 32-P-06 Tsiatouras, V.A. 29-P-06 Tsoncheva, T. 07-P-19 Tsou, J. 30-0-05 Tsubaki, S. 24-P-08 Tsubakiyama, T. 07-0-01 Tsutsumi, K. 1 l-P- 17 Tsyganenko, A.A. 12-P- 13 Tudor, M. 13-O-02 14-P-21 Tuel, A. 15-P- 17 Turnes Palomino, G. 12-P-13 24-P-15 Tvarfi~kov~i, Z. 10-0-04 Tzankarska, R. 0 I-P- 10
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395
Vos, A. 15-0-03 Vozny, V. 22-P-18 22-P-20 Vtjurina, L.M. 02-P-42 Vuono, D. 04-P- 16 Vyas, R. 24-0-04
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X Xi, C.-Y. 1 l-P- 12 Xia, J.R. 30-P-08 Xia, Q.-H. 06-P-26 Xiang, S. 02-P-15 05-P-15 12-P-15 18-P-09 20-P-12 29-P- 12 30-P-33 Xiao, F.-S. 06-P-07 12-P-07 21-O-05 27-P-07 29-P-07 Xiao, T.-C. 06-P-21 Xiao, Y.-Z. 06-P-10 Xie, G. 30-P-08 Xie, K. 02-P- 14 Xie, L. 1 l-P-13 Xin, J. 24-P-12 Xin, Q. 14-P-33 Xiong, C. 29-P-08 Xiong, G. 12-P-07 Xiu, J. 27-0-02 Xu, H. 1l-P-13 Xu, L. 05-P-17 05-P-18 24-O-01 24-P-28 Xu, Q. 22-P-09 Xu, Q.H. 1 l-P-09 22-P-08 30-P-07 Xu, R. 02-P-11 02-P-13 05-0-04 05-P-09 05-P-10 22-P-09 05-P-11 Xu, W. 11-P-I 1 Xu, Xian. 09-P08 Xu, Xin 05-P-06 Xu, Y. 05-P-20 30-P-07 Xue, J. 30-P-07 30-P-08
396
Y
Z
Yahiro, H. 14-P-09 Yamaguchi, H. 18-P- 15 Yamaguchi, T. 06-P-05 20-P-16 Yamakita, S. 02-P-28 Yamamoto, K. 2 l-P- 16 Yamashita, H. 15-P-07 28-P-07 30-P-24 Yamazaki, S. 11 -P- 17 Yan, A.-Z. 1l-P-09 Yan, B. 05-P-20 Yan, D. 18-P-07 Yan, H.S. 24-P-14 Yan, L.-J. 26-0-01 Yan, W. 05-P-09 05-P-10 Yan, Y. 20-P-11 22-0-04 Yanev, Y. 0 l-P- 13 Yang, W.-L. 21-P-06 Yang, C.M. 07-P- 13 Yang, H. 02-P-14 Yang, L. 24-P-12 Yang, M. 27-P-07 Yang, S. 12-P-06 Yang, Xu. 30-P-28 Yannakopoulos, A. 32-P-06 Yao, J. 02-P-35 Yashima, T. 27-0-01 Ye, X. 1 l-P-09 Yeramian, A.A. 14-P-14 24-P-11 Yin, Do. 29-P-08 Yin, Du. 29-P-08 Yogoro, Y. 06-P-05 Yomoda, D. 18-P- 12 Yoo, J.W. 23-P-32 Yoon, B.A. 02-P-22 Yoon, K.B. 20-0-01 Yoon, S.B. 07-P-22 York, A.P.E 06-P-21 Yoshida, H. 24-P-25 Yoshimura, M. 02-P-28 Yoshitake, H. 14-P-26 Yoshizawa, K. 28-P-07 Yu, C. 08-P-II Yu, J. 02-P-11 05-0-04 05-P-09 05-P-10 09-P0-8 22-P-09 Yu, J.-S. 07-P-22 Yu, Jia. 14-P-33 Yu, N.-T. 12-P-10 Yu, S.-F. 1l-P- 12 Yu, Y. 12-P-07 27-P-07 Yuan, H.-M. 05-P- 11 1l-P-12 Yuan, Z.Y. 06-P-09 Yue, Y. 08-0-04 08-P-08 Yuschenko, V.V. 1 l-P-06 Yushchenk, V.V. 1 I-P-23
Zaborskii, A.A. 22-P-15 Zadrozna, G. 04-P-12 24-P-22 Zakarina, N.A. 15-P- 14 Zaki, T. 18-P- 14 Zakordonskiy, V.P. 3 l-P-08 Zanardi, S. 01-K-01 Zanibelli, L. 29-0-0 Zarbaliyev, R.R. 25-P- 15 Zarkovic, N. 32-P-09 Zavoianu, R. 24-P-29 Zecchina, A. 14-P-34 15-O-05 24-P-15 Zeithammerova, J. 3 l-P-09 Zeng, X. 12-P-15 30-P-33 Zeng, Y. 17-P-06 Zenonos, C. 14-P-39 Zerbino, J.O. 20-P-14 Zeuthen, P. 26-0-03 Zha, J. 07-P-09 Zhang, A.M. 22-P-08 Zhang, D. 22-0-02 Zhang, H. 05-P-06 07-P-09 Zhang, H.Y. 12-P- 11 Zhang, J. 30-P-24 Zhang, J.Y. 11-P-22 Zhang, L. 05-P-08 22-0-02 Zhang, Luxi 29-P-08 Zhang, P. 05-P-08 07-P-07 Zhang, W. 08-P-06 Zhang, X.F. 20-P-06 Zhang, X.T. 28-0-02 Zhang, Xia. 24-P-12 Zhang, Xio. 20-P-07 Zhang, Yi. 21-P-10 Zhang, Yu. 21-P-09 Zhang, Zh. 07-P-09 Zhang, Zo. 06-P-07 Zhanpeisov, N.U. 15-P-08 Zhao, D. 05-P-06 06-P-07 07-P-09 08-P-I 1 08-P-13 Zhao, H. 22-0-02 Zhao, J.J. 22-P-08 Zhao, L. 27-P-07 Zhao, W. 29-P-08 Zhao, X.S. 07-0-05 Zhao, Z. 22-P-09 Zheng, S. 11-P-24 Zhilinskaya, E.A. 14-P- 15 Zholobenko, V.L. 12-P-16 24-P-21 Zhong, B. 06-P- 10 Zhou, H. 16-P- 16 Zhou, L.-P. I1-P-21 11-P-22 Zhou, W. 06-P-09 07-P- 17 Zhou, Y. 05-P-06
397
Zhu, G. 03-P-08 09-P0-8 Zhu, H.Y. 07-P- 18 Zhu, J.H. 18-P-07 30-P-07 30-P-08 Zhu, L. 29-P-07 Zhu, W. 18-0-04 Zhu, Z. 24-P-06 Zidek Z. 29-P-26 Zik~inov~, A. 14-P-38 24-P- 10 ~ilkov~ N. 14-P-21 14-P-22 Ziolek, M. 07-0-04 27-P-09 Zones, S.I. 02-0-05 03-0-03 1 l-P-16 17-P-07 26-0-05 Zong, B. 30-P-29 Zou, X. 09-0-03 09-P-12 Zou, Y. 02-P-11 05-0-02 05-0-02 05-P-08 II-P-11 Zu, Z. 12-P-05 Zubowa, H.-L. 2 l-P- 14 Zukal, A. 06-P-20 22-P-06 22-P-13 Zulfugarova, S. 27-P-13 Zvolinschi, A. 04-P-09
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399
SUBJECT
A AASBU method, structure prediction 07-P-21 Ab initio calculations 15-0-01 Ab initio calculations, molecular orbital 15-P-07 Ab initio cluster calculation 15-P-08 15-P-21 Ab initio simulation, dynamical processes 15-O-02 ABW beryllophosphate 05-P-06 Acetal formation 23-P-21 Acetaldehyde, aqueous 23-P-06 Acetic acid purification 18-O-05 Acetone dimerisation to MIBK 23-0-05 Acetonitrile adsorption, NMR study 13-P- 14 Acetonitrile hydrogenation 23-P-28 Acetonitrile, synthesis 10-P-08 Acetylene 19-P-07 Acetylene oligomerisation 24-P- 15 1-Acetyl-2-metoxynaphthalene isomerisation 25-P-08 Acid/base properties 10-0-02 Acid dealumination,BEA 11-P-22 Acid, hybrid mesoporous 08-P- 10 Acid leaching, zeolite Y 1 I-P-08 Acid sites 13-O-01 13-0-04 11-P-26 Acid site, enhanced strength 13-P- 10 Acid sites, FAU 13-P- 13 Acid site location, MOR 12-P-16 Acid sites, MCM-48 29-0-04 Acid sites, mesoporous silica 24-P-25 Acid strength, MeAPO-31 14-P-13 Acid treatment, clinoptilolite 0 I-P-09 Acidity 13-0-04 23-P- 15 24-0-01 Acidity-activity relationship 15-P- 16 Acidity, aluminophosphate 05-P-09 Acidity, dealuminated FAU 1 l-P-21 Acidity, EMT 13-P-21 Acidity, external surface 13-P-09 Acidity, FAU 13-P-07 13-P-21 Acidity, M4 ls 29-0-03 Acidity, mesoporous silica 08-P-06 Acidity, mordenite 12-P-05 13-P-08 Acidity, MTS 06-P-07 29-P-07 Acidity, by NH3 TPD 30-P- 18 Acidity, Pt/K-LTL 1l-P-07 Acidity, SAPO 23-P-31 Acidity, SAPO-34 24-P-26 Acidity, zeolites 19-P-07 28-P- 15 Acidity, zeolites by NMR 13-P-23 Acidity, zeolite Y 15-P- 16
INDEX
Acidity, Zr-HMS Activated sludges Activation, catalyst, by plasma Activation energy, proton jumps Activation, MFI large crystals Active sites Activity profile, granular catalyst Activity-acidity relationship Adjuvant in therapy Adsorbate configuration, bipyridine/MFI Adsorbed phase ordering, AEL Adsorbed phase, phase transition Adsorption 17-0-03 Adsorption on adsorbed surfactant 06-P-27 Adsorption, alkanes, silicalite- 1 Adsorption, Ar/N2 mixtures Adsorption, aromatics 19-0-02 Adsorption, aspirin on clinoptilolite Adsorption, binary, organics Adsorption, chloroalkanes, Ag-FAU Adsorption, chloroalkenes Adsorption, chloroform Adsorption, CO 15-P-10 Adsorption, CO2 18-0-01 Adsorption, CO2 on Cu, Zn-FAU Adsorption complexes Adsorption complexes, geometry Adsorption, dibenzothiophene Adsorption dynamics Adsorption enthalpies, Ar/N2 Adsorption, H2 Adsorption, H20, MCM-41 Adsorption, human bile Adsorption, hydrocarbons 17-P-07 18-0-04 Adsorption, isosteric heats Adsorption isotherms, modelling Adsorption, liquid phase 18-O-02 18-P-07 Adsorption, mesoporous silicas Adsorption models 16-O-03 Adsorption, modelling 19-O-02 16-P-06 Adsorption in MOR, modelling Adsorption, mycotoxins Adsorption, p-nitroaniline Adsorption, N-nitrosamine Adsorption NMR, toluene/Na-X ,Adsorption, organics 14-P-30 Adsorption, pheromones
26-P-22 31-P- 14 1 l-P- 14 15-0-01 14-P-38 12-P-08 28-P-12 15-P- 16 32-P-09 14-P-24 17-O-03 17-0-02 17-P- 17 32-0-04 19-P- 10 17-P- 15 18-P-08 32-P-08 18-P- 15 24-P- 19 17-P- 11 16-P- 14 12-P-13 18-P- 10 17-P-14 12-P-08 14-P-07 18-P- 11 19-P-07 17-P- 15 17-P- 10 17-P- 13 32-0-03 30-P-32 17-P- 14 16-P- 10 28-P-10 17-P- 12 26-P-20 16-P-14 15-P-12 32-0-04 13-P-06 18-P-07 13-P- 16 17-P-06 32-0-05
400
Adsorption of probe molecules 13-0-04 Adsorption properties, Na,Ca-LTA 17-P-09 Adsorption, proteins 23-P- 17 Adsorption, reactive 18-0-05 Adsorption, supercritical 17-P-05 17-P- 16 AEL, commensurate phases 17-0-03 Affinity index 17-P-06 AFI, Co 04-P- 13 AFI single crystal 2 l-P-08 AFM PL-2 02-0-05 AFM, growth surface SSZ-24 13-P- 16 Ag diffuse reflectance 0 l-P- 15 Ag dispersion, effect on SCR 30-P-28 Ag-clinoptilolite 0 l-P- 15 Ag-FAU 18-O-05 24-0-02 24-P-19 Ag-FER spectroscopy 14-0-03 AgI clusters in LTA 22-P- 17 Ag-LTA 14-O-04 Ag-MFI 30-0-03 30-P-28 30-P-34 Ag-MFI spectroscopy 14-0-03 Ag-MFI, adsorbent for CO 15-P- 10 Ag-MFI, deNOx catalyst 30-P-34 AgS2 clusters in LTA 14-O-04 Ag§ local structure 30-P- 16 Agglomerated nanocrystals, reactivity 03-P- 14 Aggregates, silica, fractal 14-P-25 Aging 02-0-02 Aging, effect on synthesis 02-P- 19 02-P-21 Aging, MCM-41 synthesis 06-P-21 27A1-13Cdipole interaction 13-0-01 27A1chemical shifts 15-P-21 27A12D NMR 13-P- 19 27Al(19F) WISE NMR 08-0-04 27A1MQ MAS NMR 13-O-03 13-P-20 14-P-11 27A1 NMR 07-P-08 06-P- 17 09-0-02 09-P- 11 1 I-P- 10 11-P-28 13-P- 18 13-P-22 13-P-24 18-P-13 21-P-17 30-P-19 AI coordination, AIPO4-20 09-P-11 AI distribution by cation siting 13-P-19 AI distribution in MFI 13-O-02 AI, extraframework 13-P- 18 AI, extra-framework, modelling 15-P-21 AI insertion, CON and DON 1 I-P-16 AI isopropoxide, MCM-41 secondary treatment 23-P-33 beta-Al methylphosphonate, crystallisation 21-P-17 AIMepO-beta, water adsorption 09-P- 14 AI-MCM-22 14-P-21 AI-MCM-41, catalyst support 24-P-08 AI-MCM-41, stability 06-P- 19 AIOH hydroxyls 14-P- 10 AI ordering 13-0-01 AI ordering, dachiardite 0 l-P-07 AI pentacoordinated 13-P- 18 A1 phosphites, microporous 05-P- 15 AIPO4, s e e a l s o aluminophosphate
AIPO4 deNOx catalysts 30-P-31 AIPO4 heteronuclear NMR 13-P-24 AIPO4 substituted, multipole moment 15-P-27 AIPO4 synthesis, templates 02-P-33 AIPO4, synthesis intermediate 02-P-11 AIPO4-5 13-P-14 AIPOa-5/DCM resin composites 21-O-04 AIPO4-5 with Fe 14-P-39 AIPO4-5 host 21-O-05 21-P-08 A1PO4-11, adsorbed phase ordering 17-O-03 AI PO4-14, hydration 13-P-20 AIPO4-18 with Fe 14-P-39 AI PO4-18, hydration 13-P-20 AIPO4-20 09-P- 11 AIPO4-20, host 22-P- 19 AIPO4-31, substituted 14-P- 13 AIPO4-34, hydration 15-P- 17 AIPO4-CJ2, NMR crystallography 09-0-02 AI quantification 13-0-03 AI-SBA- 15, synthesis 08-0-04 AI sources, MCM-41 06-P- 17 AI support, MFI films 20-P-I 7 AI-Mn phosphate 05-P-11 AI, traces in TS-1 27-0-02 Alcohol oxidation 27-P-08 Aldehyde, unsaturated 29-P- 15 Aldol condensation 23-P-23 Alkali cations, effect on adsorption 32-0-05 Alkali cations, effect on photocatalysis 15-P-07 Alkali cations, effect in synthesis 03-0-05 Alkali cations in FAU, EPR 14-P-07 Alkali cations in fluoride media 04-P-17 Alkali cation templates 03-P- 18 Alkali-exchanged LSX 14-0-02 Alkali-exchanged MCM-22 and MCM-36 10-O-02 Alkali metal particles/FAU 14-P-37 Alkali treatment, bentonite 03-P-06 Alkali treatment, MFI 1 l-P-30 Alkaline earth in LTL synthesis 02-P-17 Alkalinity, effect on crystallisation 03-P-19 Alkane activation 25-0-05 25-P-15 Alkane conversion 15-P- 15 Alkane cracking 15-P- 15 Alkane diffusion, silicalite- 1 19-P- 10 Alkane formation, free energy 16-0-01 Alkane hydroconversion 16-0-01 Alkane isomerisation 26-0-02 n-Alkanes, long chain, isomerisation 26-P-23 Alkanes, oxidation 27-0-01 27-P-06 Alkene, s e e Olefin Alkoxy surface species from dechlorination 24-P-19 Alkoxysilanes 1 l-P-09 Alkoxysilane CVD 11-O-02 Alkylamine 06-P-23 Alkylammonium in AIPO4 synthesis 02-P-33 Alkylation 06-P-06 24-P-09 25-P-16 Alkylation, aniline 23-P- 12 25-P- 11
401
24-P-06 25-P-15 29-0-01 Alkylation, benzene 25-0-05 Alkylation, benzene, by alkanes 25-P-0 29-P-11 Alkylation, biphenyl 25-P-12 Alkylation, bulky aromatics 28-P-08 Alkylation, ethylbenzene 24-P-20 Alkylation, isobutane 25-P-16 Alkylation, isopropylnaphthalene 25-0-03 25-P-13 Alkylation, naphthalene 28-P-15 Alkylation, orthoAlkylation, phenol 23-P-31 25-P-09 28-P-15 Alkylation, polyaromatics 25-O-01 25-P-06 25-P-09 25-P-14 Alkyl hydroperoxide, decomposition 27-P- 10 Alkyl ketone photolysis 15-P-07 N-alkylphenothiazines, photoionisation 24-P-07 Alumina, anatase stabilizer 22-P- 13 Alumina membrane support 20-0-03 Alumina, mesoporous 06-P-23 07-P- 16 07-P- 18 07-P-08 Alumina, mesostructured 02-P-19 Alumina source 30-P-19 Alumina support 07-P-09 Alumina-zirconia, mesoporous 11-P-22 Aluminate, sodium reagent 1I-P- 10 11-P-22 Alumination, BEA 23-P-33 25-P-12 Alumination, MCM-41 29-0-04 Alumination, MCM-48 11-P-28 Alumination of siliceous zeolites Aluminophosphates, s e e also AIPO4 03-P-16 14-P-22 14-P-33 Aluminophosphate, anionic 05-P-09 Aluminophosphate, chiral 05-P- 10 Aluminophosphates, hydration 15-P- 17 Aluminophosphate, lamellar 02-P- 11 Aluminophosphates, lattice vibrations 14-P-31 Aluminophosphate MIL-34 05-P- 19 Aluminophosphates, Ni 09-P-08 Aluminosilicate MCM-41 06-P-08 07-P-14 24-0-05 24-P-22 Aluminosilicate, mesoporous 06-P-07 06-P-15 06-P-22 06-P-27 08-P-06 08-P-14 29-0-04 1 I-P-16 Aluminosilicate UTD- 1 1l-P-16 Aluminosilicate SSZ-33 04-0-05 AM- 13, vanadosilicate 04-0-05 AM- 14, vanadosilicate 02-P-33 Amides in phosphate synthesis 11-P-25 Amination, methanol 23-P-07 Amination, octanoi 05-P-06 Amines in beryllophosphates synthesis 06-0-04 Amine expander for MCM-48 06-P- 11 Amine extraction from HMS 02-P-33 Amines in phosphate synthesis Amine, template 02-P-41 03-0-03 07-0-05 Amine, zeolite template 05-0-02 Amino acids 18-0-02 Amino acids separation 28-P- 10 3-Aminopropylsilane grafting 29-P-31 Ammonium exchange, clinoptilolite 0 I-P- 12
Ammonium removal 3 I-P-09 31-P-11 31-P-12 31-P-15 Ammoxidation, ethylene Amorphisation at high pressure Amorphous aluminosilicate Amorphous aluminosilicate, zeolitic Analcime crystal chemistry Analcime from fly ash Anatase, aggregated nanocrystals Angle BOT-chemical shift correlation Aniline methylation Aniline, N-methylation Animal feeding 32-P-06 32-P-10 Anion exchanger Antarctica, zeolite occurrences Anthraquinone/BEA photocatalyst Anticancer activity Apatite, crop enhancement APO-CJ3 APO-CJ4 Apple fragrance Aquaculture Aqueous solution Ar adsorption Ar adsorption, AEL Ar, supercritical adsorption, zeolites Ar/N2 adsorption, FAU Ar/N2 adsorption, LTA Armenia, natural mordenite Aromatics, adsorption Aromatics, adsorption on MFI Aromatics, bulky, alkylation Aromatic chloro compounds Aromatics, diffusion Aromatics disproportionation Aromatics hydroalkylation Aromatics hydrodecyclisation Aromatics, hydrogenation Aromatics hydroxylation Aromatics, nitration Aromatics oxidation Aromatics oxyhalogenation Aromatisation, C4 hydrocarbons 24-P-30 Aromatisation, cyclohexane Aromatisation, cyclohexene Aromatisation, n-hexane 15-P-09 Aspirin Aspirin adsorption on clinoptilolite ATO, substituted ATO, substituted, synthesis Au nanoparticles Au, bimetallic clusters in FAU Au2CI6 encapsulated AV-6, stannosilicate AV-7, stannosilicate Avoidance rule Azamacrocycles in synthesis
3 l-P- 10 31-P-16 10-P-08 16-P- 19 02-P-32 29-P- 12 01 -P- 11 18-P- I 0 22-P- 13 13-P-I 1 23-P- 12 25-P-11 32-P-11 22-P- 12 0 l-K-01 27-P- 14 32-P-09 31-O-02 02-P- 11 05-P- 10 23-P-22 3 l-P- 12 01 -P- 17 17-P-05 17-0-03 17-P-I 6 17-P- 15 17-P- 15 0 I-P- 16 19-0-02 13-P-25 25-P- 12 23-P- 16 19-0-02 11-O-02 23-P-21 26-P- 13 26-P- 10 2 I-P-07 13-P-22 2 l-P-07 23-P-24 24-P-31 24-P-27 24-P-27 28-0-02 32-P-07 32-P-08 14-P- 13 04-P-09 11-O-01 11-O-01 10-0-03 05-P- 13 05-P- 13 0 I-P-07 05-0-03
402
Aziridination, olefins Azo dyes
24-0-04 21-O-02
B liB NMR 13-P-11 11B, quadrupolar interaction 13-P- 11 B distribution in MFI 13-O-02 BN nanoparticles 21-O-05 B ordering 13-0-01 B-substituted zeolites 13-P- 11 B-treated zeolites 11-P-23 Ba in alkaline synthesis 02-P-17 Ba-X, adsorbent 16-0-03 Basic catalysis 02-P-22 04-0-02 10-O-02 23-P-13 23-P-23 Basic catalysis, zincophosphates 29-P-23 Basic catalyst, immobilised 23-0-04 Basic catalysts, mesoporous 29-P- 10 Basic catalyst, MIBK synthesis 23-0-05 Basic probe molecules 13-P- 13 Basic zeolites 10-O-02 23-P-12 23-P-13 23-P-29 29-P-20 Basic zeolites, synthesis 04-0-02 Basicity of zeolites by NMR 13-P-23 Basicity, zeolite oxygen 14-O-02 BEA, adsorbent 18-0-02 BEA, A! distribution 13-P- 19 BEA, alkylation catalyst 24-P-06 24-P-20 25-0-02 25-P-07 25-P-09 25-P-13 25-P-14 02-P-35 BEA, all-silica, synthesis 20-P-18 BEA/alumina membranes 1 I-P-10 11-P-28 BEA, alumination 27-P-14 BEA, anthraquinone photocatalysts 24-0-04 BEA, aziridation catalyst 28-P- 11 28-P- 15 BEA, catalyst 20-P-12 BEA/ceramic composite membrane 04-P-08 BEA, Cr 02-P-23 BEA, crystallisation kinetics 11-P-22 BEA, dealumination and realumination 30-P-26 BEA-DLH oxidation catalyst 32-0-05 BEA, drug carrier BEA, effect of hydrophobicity on activity 28-P-14 28-P-14 BEA, esterification catalyst BEA, Fe 04-P-07 10-O-04 30-P-11 30-P-27 BEA, Fe, DeNOx catalyst 30-P-06 BEA, flexible lattice 13-P-22 BEA, Ga 03-P- 10 BEA, hydroconversion catalyst 24-0-03 BEA, In deNOx catalyst 10-O-01 BEA, isomerisation catalyst 24-P-16 25-P-0 26-O-01 28-P-13 BEA, lattice vibrations 12-P-07 BEA, macroporous structures 2 l-P- 15 BEA, Mo 14-P-08
BEA, NiMo hydrotreatment catalyst 26-P-15 BEA, partially crystalline 29-P-12 BEA, photocatalyst 30-P-20 BEA, polystyrene beads 2 l-P-12 BEA, polytypism 0 l-K-01 BEA, Pt 17-P-08 BEA, Pt aromatisation catalyst 15-P-09 BEA, Pt hydrogenation catalyst 26-P-13 BEA, Pt isomerisation catalyst 20-P-18 BEA, Pt/Cs 26-0-05 BEA, ring opening catalyst 26-0-03 BEA, silylation 1 l-P-09 BEA, synthesis, with DLH 30-P-26 BEA, Ti 27-P- 11 27-P- 17 BEA, V 14-P-35 Beckmann rearrangement 15-0-05 23-0-03 23-P-18 23-P-21 23-P-27 27-P-16 Bentonite adsorbent 32-0-04 Bentonite application 18-P- 14 Bentonite, pillared 22-P- 16 Bentonite zeolitisation 03-P-06 Benzaldehyde-ethylcyanoacetate condensation 23-0-04 Benzaldehyde, trimethylsilylcyanation 23-P- 11 Benzene adsorption 14-P- 14 18-P- 15 Benzene adsorption, MFI 17-0-02 18-P-08 Benzene alkylation 24-P-06 25-0-05 25-P- 15 29-O-01 Benzene diffusion, NMR imaging 19-K-01 Benzene hydroconversion 26-P- 15 Benzene hydrogenation 27-0-04 Benzene oxidation to phenol 27-0-03 Benzene removal, membrane 20-P- 12 Benzothiophene HDS 26-P-07 N-benzyl- l-azoniumbicyclo[2,2,2]-octane template 03-0-04 Beryllophosphate synthesis 05-P-06 Beryllosilicates 05-O-05 Beta cage, encapsulation modelling 15-P-08 Bifunctional catalysis 23-0-05 23-P-14 23-P-28 24-0-03 25-P-15 26-P-06 Bifunctional catalysts, MCM-41 26-P-18 Bifunctional catalysts, Pt,Ni-USY 14-P-36 Bile, adsorption 32-0-03 Bilirubin 32-0-03 Bimetallic catalysts 22-0-05 29-P-15 Bimetallic catalyst, Pt,Ni-USY 14-P-36 Bimetallic clusters with Au 11-O-01 Bimodal pore structure 06-P-20 Bimodal porosity, MFI 03-0-02 Binary adsorption 17-P- 15 18-P- 15 Binder, polymeric 22-P- 15 Biological wastewater treatment 3 l-P- 14 Biomedical applications 32-O-01 32-P-09 Biomimetic oxidation transfer 27-P- 10 Biphasic system, membrane separation 23-P-10 Biphenyl adsorption, MFI 14-P- 18
403
Biphenyl alkylation 25-P-07 25-P-09 25-P-14 29-P- 11 29-P-11 Biphenyl isopropylation 16-P-08 Biphenyl isopropylation, models 14-P-24 2,2'-Bipyridine adsorption/MFI 24-P-29 Bipyridine complex, encapsulated 08-P-12 Block copolymer surfactants 16-0-05 Boggsite, Xe-SF6 diffusion, modelling 13-P-11 Borates NMR 09-P-12 Borogermanates, layered 13-P-11 Borosilicates NMR 1 l-P-16 Borosilicate zeolites 26-0-05 Borosilicate zeolite reforming catalyst 13-P-25 Branched paraffins, adsorption on MFI Breakthrough curves 18-P- 15 19-P-06 24-0-04 Bromamine-T Bronsted acid sites 12-P-16 13-O-01 13-P-17 13-P-18 14-P-21 Bronsted acid sites in ZSM-5 13-P- 10 30-P-25 Bronsted acidity 05-P-09 1 I-P-07 13-P-19 14-P-23 Br~nsted acidity, EMT 24-P-15 Br~nsted acidity, ETS- 10 14-P-23 Bronsted acidity, FAU 13-P-05 Bronsted acidity, HPA Bulgaria, zeolite occurrences 0 l-P- 10 01-P-13 Bulk-material dissolution in MFI synthesis 02-P-26 22-0-03 Butadiene dehydrocyclodimerisation 24-P-09 Butane activation 24-0-01 n-Butane dehydroisomerisation n-Butane isomerisation 24-P- 16 29-P-17 24-P-20 2-Butene in alkylation Butene isomerisation 14-P-22 24-P-21 24-P-17 l-butene synthesis 05-P-17 Butylamine templates 23-P-23 n-Butyraldehyde aldol condensation
C 13C chemical shift anisoptropy 13C MAS NMR ~3C MAS NMR, molecular dynamics 13C NMR 03-0-04 09-P-11 13-P-16 23-P-12 ~3CNMR, MFI synthesis ~3CNMR probe, nitromethane t3C-27AI dipole interaction C4 hydrocarbons aromatisation C5-C7 olefins isomerisation C5-C6 hydroisomerisation C6 isomer diffusion C60 CF4-CH4 diffusion in FAU, modelling CH4 activation CH4 adsorption, AEL CH4 conversion
13-P-16 13-P-06 30-P-19 02-P-40 23-P-13 13-O-01
24-P-30 26-P-09 20-P-18 19-P-10 1 l-P-12 16-O-05 24-0-02 17-O-03 24-0-02
CH4 in deNOx SCR 10-O-01 30-P-28 CH4, photocatalytic oxidation 24-P- 12 CH4, supercritical adsorption, zeolites 17-P- 16 CH4-CF4 diffusion in FAU, modelling 16-O-05 Ca in LTL synthesis 02-P-17 Ca promoters, DeNOx 30-P-25 CaClz/Silica Gel 31-O-04 Ca,Na-LTA 17-P-09 Cadmium clusters 09-P-06 Cadmium exchange 3 l-P-08 Cafeine separation 20-0-05 Calcination, exchanged zeolites 10-P-07 Calcination, mordenite 12-P-05 Calcination, by ozone 11-P-27 Calcination, partial 1l-P-12 Calculations, ab initio 15-P- 14 Calculation, framework vibrations 14-P-34 Calculations, semiempirical 15-P- 14 Calixpyrrole synthesis 28-0-04 Calorimetric sensors 22-P-11 Calorimetry 31-O-04 Cancrinite synthesis 02-P-07 03-P-I 1 Cancrinite/sodalite overgrowth 02-P-28 Capillary columns, LTA 18-P-09 Caprolactam 23-P- 18 23-P-27 27-P-16 Carbanium cation 24-P-09 Carbenium ions 12-P-06 Carbocation 15-P- 15 Carbon intercalation 1 l-P-11 Carbon nanotubes 21-P-08 Carbon nanotubes, formation 22-P-08 Carbon number, effect on SCR 30-0-03 Carbon replica 07-P-22 Carbon templates for MFI mesopores 03-0-02 26-0-02 Carbon, mesoporous PL-1 07-O-01 07-P-22 29-P-13 Carbonisation 07-P-22 Catalyst deactivation 27-P- 16 Catalyst engineering 28-P- 12 Catalyst heterogeneity 23-0-02 Catalytic activity, external surface 13-P-09 Catalytic cracking 08-P- 13 Catalytic tests of acidity and basicity 13-P-23 Catalytic test reactions 26-P-11 Catalysis, see individual reactions Catalysis, effect of microwaves 28-0-02 Catechol 27-P- 17 Cation distribution, MOR 16-P-11 Cation distribution, Na,Ca-LTA 17-P-09 Cation effect on aromatisation 15-P-09 Cation effects in gas separation 18-O-03 Cation effect in microwave heating 11-P-I 3 Cation exchange 0 I-P- 17 09-0-05 10-0-02 10-P-05
1 l-P- 18 1 l-P- 19 2 l-P-07 3 l-P-05
31-P-06 31-P-08 31-P-10 31-P-15 31-P-16
404
Cation exchange, clinoptilolite 01-P-12 01-P-17 22-P-12 Cation exchange, drying effect Cation exchange, ETS-4 Cation exchange, FAU Cation exchange, indium Cation exchange, PHI Cation exchange, solid state 10-O-01 10-P-06 10-P-08 Cation exchange, SOMS Cation impurities, EPR Cation location Cation location, clinoptilolite Cation location, In-X Cation location, MOR Cation mobility, high temperature Cation properties, modelling Cation radicals Cation radicals, biphenyl/MFI Cation sites Cation sites, MFI Cation sites, modelling Cations sites by UV-visible spectroscopy Cd clusters Cd(l-x)Mn(x)S Cd-X Ce,EU silicates Ce and Pd promoter Ce-MCM-41 Ce-MCM-41, stability Ce-MFI Ce-MFI, oxihalogenation catalyst Ce-MOR Cellular reactions Cement-zeolite composite Ceramic support Ceramic from zeolites CHA CoAPO CHA from fly ash CHA, acidity, modelling Chabazite, rare earth Chabazite/sodalite overgrowth Chelate post-treatment Chelators, Fe Chemical liquid deposition Chemical shift and electric gradient Chemical shift-geometry correlation Chemical shift ~70-angle relationship Chemisorption Chiral hydrogenation Chiral molecular sieve Chiral templates Chiral Ti (IV) Salen complex Chlorination, diphenylmethane Chloroalkane adsorption, Ag-FAU Chloroalkenes on MFI Chloroaromatics dechlorination
22-P-15 1 l-P-20 1 l-P- 15 17-P-14 30-P- 15 01-O-05 30-P-27 05-0-01 14-P- 15 15-P- 11 01-O-03 09-P- 10 09-P- 13 14-P- 17 15-P-08 13-P-08 14-P- 18 03-0-03 15-P-24 15-P-23 14-O-03 09-P-06 21-O-03 09-P-06 05-P- 12 30-P-22 07-P-23 06-P- 19 23-P-24 23-P-24 29-P-11 32-P-09 3 l-P- 13 20-P-09 10-P-07 04-P- 13 18-P- 10 15-0-01 1 I-P-19 02-P-28 11-O-04 32-0-02 11-P-24 14-P-27 13-P- 11 14-O-02 17-P-08 23-P-25 05-P- 10 05-0-04 23-P-11 23-P-30 24-P- 19 17-P-I 1 23-P- 16
Chlorocarbon oxidation 30-P- 18 Chlorocarbon removal 30-0-05 Chiorofluorocarbon decomposition 30-P- 19 Chlorofluorocarbon-zeolite interaction 30-P- 19 Chloroform adsorption 3 l-P-08 Chloroform, adsorption in Na-Y 16-P- 14 Cholesterol 32-0-03 Chromatography, LTA column 18-P-09 Chromatography, MSU-X application 08-O-01 Chromatography, stationary phases 18-P-06 Cigarette smoke 30-P-07 Cinchonidine 23-P-25 Cinnamaldehyde hydrogenation 07-P- 16 Cinnamate ester synthesis 23-0-02 Cinnamyl alcohol 25-P-12 Circular crystals, mesoporous silica 06-0-02 CIT-5 (CFI), Fe 16-P-09 Citology 32-0-02 Citric acid, complexing agent 04-P- 15 CI-CIO hydrocarbons in SCR-NOx 30-0-03 Clays, polymer degradation catalyst 30-P-17 Clear solution synthesis 02-0-04 Clinoptilolite, acid sites 11-P-26 Ciinoptilolite, acid treatment 0 l-P-09 Clinoptilolite, acidity 23-P-09 Clinoptilolite adsorbent 32-P-08 Clinoptilolite, Ag 0 l-P- 15 Clinoptilolite, applications PL-2 3 l-P-07 3 l-P-08 3 l-P-10 31-P- 14 31-P-15 32-0-03 32-P-10 32-P-11 0 l-P- 10 Clinoptilolite, Bulgaria 32-0-03 Clinoptilolite, Ca Clinoptilolite, cation exchange 01-P-12 31-P-12 32-0-04 3 l-P-09 Clinoptilolite, cation exchanger 31-O-02 Clinoptilolite, crop enhancement 1 l-P-20 30-P- 10 Clinoptilolite, Cu 23-P-09 Clinoptilolite, dehydration 23-P-08 Clipnotilolite dehydration catalyst 30-P-10 Clinoptilolite, deNOx catalyst 19-0-04 Clinoptilolite, diffusion 32-P-09 Clinoptilolite and health 22-P-10 Clinoptilolite, host Clinoptilolite, hydrothermal transformation 32-P-07 3 l-P-06 Clinoptilolite for lead removal 32-P-12 Clinoptilolite, medical applications 32-0-04 Clinoptilolite, modified, adsorbent 01-O-02 Clinoptilolite, occurrences Clinoptilolite, organic-modified 22-P- 12 22-P-15 27-P-08 Clinoptilolite, oxidation catalyst PL-2 Clinoptilolite properties 32-P-07 Clinoptilolite, purified 01 -O-03 Clinoptilolite stability PL-2 Clinoptilolite, structure 11-P-26 Clinoptilolite thermal behaviour Clinoptilolite tuff 01-P-09 01-P-12 01-P-13 31-P-11
405
Cloverite, host 2 l-P- 14 Cluster calculations 15-P-09 Clusters, in LTA 22-P-17 CMK- 1 mesoporous carbon PL-1 J33Co MAS NMR 09-0-05 Co 2+ in AIPO4 04-P- 11 04-P- 13 CoAPO, deNOx catalysts 30-P-31 CoAPO-5 04-P-13 CoAPO-5, sensors 22-P-11 CoAPO- 18, Co site 14-0-05 CoAPO-31 14-P-13 CoAPO-31, synthesis 04-P-09 CoAPO-34 29-P-14 CoAPO-34, Co site 14-0-05 CoAPO-44 04-P- 13 CoAPSO-31, synthesis 04-P-09 Co, cation site 15-P- 11 Co-ERI, oxidation catalyst 27-P- 13 Co-FER catalyst 30-P-35 Co histidine complexes 27-P- 10 Co-HMS 29-P-08 Co 2§ ion probes 14-P-21 Co-MCM-22 14-P-21 Co-mesoporous silica 08-0-02 Co-MFI 04-P- 18 13-0-02 30-0-03 Co-MFI, deNOx catalyst 30-P-34 Co-MFI, by solid state ion exchange 10-P-08 Co-MOR, oxidation catalyst 27-P- 13 Co, Ni promotion 26-P-17 Co, Pd, Ce trimetallic catalysts 30-P-22 Co 2§ probe of AI distribution 13-P- 19 Co Salen complexes on MCM-41 23-P-10 Co site in CoAPO 14-O-05 Co spinel from zeolites 10-P-07 Co, tungstophosphates 05-P-20 Co UV-Vis 04-P-18 13-P-19 Co XPS 04-P- 18 Co-zeolites, oxidation catalysts 27-P-08 Co-zeolite Y, oxidation catalyst 27-P-13 CO adsorption 13-0-04 CO adsorption equilibria 12-P- 13 CO adsorption, AEL 17-O-03 CO adsorption, Ag-MFI 15-P- 10 CO adsorption/cation MFI 15-P-24 CO adsorption, Cu-MFI 14-P-40 CO adsorption, EMT 14-P-23 CO adsorption, FAU 14-P-23 CO adsorption, Pt-zeolites 17-P-08 CO hydrogenation 24-P-11 CO oxidation 29-P- 14 30-P- 10 CO reduction, MeAPO-34 29-P-14 CO2 adsorption, Cu, Zn-FAU 17-P-14 CO2 adsorption isotherms 17-P- 14 CO2 adsorption on zeolites 18-P- 10 CO2+H2 reaction 24-P-26 CO2 and refining PL-4 CO2 removal 18-0-01
CO2 separation CO2, supercritical solvent Coating Coating by LTA Coating, MFI/gold Coating by zeolites, Al alloy Coating, zeolites/diatoms Coke Coke, effect on catalysis Coke, effect on isomerisation Coke formation, MFI Coke selectivation Coke tolerance Coking, in MTO Cold start exhaust gases Colloidal FAU crystals 02-0-03 Colloidal MFI crystals Colloidal offretite Colloidal templates Combinatorial chemistry Combinatorial methods in synthesis 03-K-01 03-P-13 03-P-16 03-P-18 Commensurate phases, in AEL Compass forcefield Complexing agent Complexing agent, citric acid Composite, BEA/polystyrene 2 l-P- 12 Composite, diatom/zeolite Composite, LTA/polystyrene Composite, LTL/FAU Composite membrane, BEA/ceramic Composite membrane, MFI/ceramic Composite nanotube/AIPO4-5 Composite, resin-silicate Composite, zeolite-cement Composite, zeolite/polymer Composite zeolitisation Composite, ZSM-5/Raney metal Computational analysis 16-P-08 Confined system, 1-dimensional Confined systems, phase transitions
18-0-01
20-0-05 20-P-09 20-P-15 20-P-14 22-0-04 21-P-07 24-P-06 30-P-21 25-P-08 24-P-31 28-P-06 26-P-16 24-P-28 30-P-32 02-P-14 02-0-04 02-P-12 07-P-22 03-P-12 06-P-25 17-O-03 16-P-06
03-P-08 04-P- 15 21-P-15 21-P-07 21-P-12 07-P-10 20-P-12 20-P-12 2 l-P-08 03-P-07 31-P-13 19-0-05 21-P-07 30-P-29 16-P-15 17-P-17
17-O-01 17-P-17
Conformational analysis Congo red in MCM-41 Connectivities, by MQ MAS NMR Contaminant concentration Continuous microwave synthesis Conversion, polyethylene Cordierite support 12-P- 15 20-P- 13 Correlation functions Corrosion pevention 06-P-09 Cosurfactants CrAPO-5, synthesis Cr-BEA Cr cation exchange Cr ETS- 10 Cr-HMS
16-P-17 22-P-21 13-P-24 31-P-08 03-P-15 24-P-13 30-P-33 16-P-18 22-0-04 06-P- 18 04-P-12 04-P-08 31-P-13 27-P-15 28-P-07
406
06-P-12 Cr-MCM-48 23-P-24 Cr-MFI 27-P-06 Cr, oxidation catalyst 31-P-13 Cr removal from wastewater 31-P-13 Cr storage 27-P-08 Cr-zeolites, oxidation catalyst 23-P-24 Cr-ZSM-5, oxihalogenation catalyst 15-P-15 Cracking, alkanes 11-P-23 Cracking catalyst, treated USY Cracking, cumene 03-P- 14 04-P- 14 1 l-P-30 28-P- 16 29-P-07 26-P-10 Cracking, cyclic oils 26-P-11 Cracking, methylcyclohexane 24-P-06 Cracking, n-heptane 08-P-13 Cracking, n-hexadecane Cracking, n-hexane 26-0-01 29-P-26 24-P-13 Cracking, polyethylene 30-P-17 Cracking, polymers 15-P-22 Cracking, thiophene, modelling 29-P-07 cracking, 1,3,5-trisopropylbenzene 28-P-13 m-Cresol transformation Croatian clinoptilolite 0 I-P- 17 31-P-11 Crop enhancement 31-O-01 31-O-02 29-P-15 Crotonaldehyde, hydrogenation 29-P-15 Crotyl alcohol, synthesis 06-0-02 Crystals, circular, mesoporous silica 01-P-11 Crystal chemistry, analcime 20-P-16 Crystal growth, FAU 20-P-16 Crystal growth, LTA 02-P-09 Crystal growth, MFI 02-P-08 Crystal growth rate 02-P-37 Crystal growth, ultrasound monitoring 19-O-04 Crystal morphology, effect on diffusion 02-P- 17 Crystal morphology, LTL 16-P-16 Crystal morphology, TS- 1 20-0-04 Crystal orientation 02-P-23 Crystal size, BEA 24-P-16 Crystal size, effect on catalysis 02-P- 17 Crystal size, LTL Crystal size, MFI 02-P-09 02-P-15 04-P-10 Crystal size, Nb-MFI 04-0-04 Crystal size tayloring 09-P-14 Crystal structure, AlMepO 09-P- 11 Crystal structure, AIPO4-20 09-P-06 Crystal structure, Cd-FAU 09-P-07 Crystal structure, Cu molybdate Crystal structure determination 01-K-01 05-P-19 09-P-13 09-P-12 Crystal structure, layered germanate 05-0-01 Crystal structure, SOMS 29-P-12 Crystallinity, partial, BEA 02-P-20 Crystallisation 21-P-17 Crystallisation, AIMepO 03-P-18 Crystallisation fields 03-0-05 Crystallisation fields, K-Na system 02-P-37 Crystallisation, in-situ monitoring 02-P-23 Crystallisation kinetics, BEA
04-P- 16 Crystallisation kinetics, ETS-4 02-P-21 Crystallisation kinetics, KFI 02-P-29 Crystallisation, LTA 02-P-40 Crystallisation, MFI, phosphate-affected Crystallisation models 02-P-24 02-P-31 03-P-19 Crystallisation, mordenite 02-P-40 Crystallisation promotor, phosphate 02-P-30 Crystallisation, rapid 02-P-16 Crystallisation, silicalite- 1 02-O-05 Crystallisation, SSZ-24, AFM 16-P-06 Crystallography 133CsNMR 14-P-17 26-0-05 Cs-BEA, Pt 1 l-P-18 Cs cation exchange 23-0-05 Cs-FAU, Pt catalyst Cs,Na-FAU 14-P-I 7 29-P-20 29-P-20 Cs,Na-MFI 23-P-29 Cs-zeolite condensation catalyst 30-P-31 Cu in AIPO4, deNOx catalyst 14-P-40 Cu carbonyl complexes 1 l-P-20 Cu § cation Cu, cation exchange 1 l-P-20 31-P-08 15-P-11 Cu § cation site Cu 2+, cation site 15-P-11 30-P-10 Cu-Clinoptilolite Cu+-Cu2+ pairs in Cu-MFI 14-P-40 27-P-13 Cu-ERI, oxidation catalyst 12-P-09 Cu-exchanged zeolites 17-P-14 Cu-FAU Cu-FAU oxidation catalyst 27-P-13 30-P-23 24-P-23 Cu-FAU reforming catalyst 14-O-03 Cu-FER spectroscopy 27-P-10 Cu histidine complexes 29-P-08 Cu-HMS 07-0-04 Cu-MCM-41 04-0-01 Cu methylamino complexes Cu-MFI 04-0-01 12-P-15 13-O-02 15-P-13 30-0-03 30-P-09 30-P-33 24-P-30 Cu-MFI, aromatisation catalyst Cu-MFI, deNOx catalyst 16-P-20 30-P-14 30-P-21 Cu-MFI diffuse reflectance spectroscopy 15-P-13 Cu § in MFI framework 15-P-13 Cu 2+ in MFI framework 27-P-12 Cu-MFI oxidation catalyst 14-O-03 Cu-MFI, spectroscopy 14-P-40 Cu-MFI, synthesis 09-P-07 Cu molybdate structure 1 l-P-20 Cu-MOR 27-P-13 Cu-MOR, oxidation catalyst 12-P-09 Cu,Na-Y 24-P-26 CuO-ZnO-ZrO2 27-P-06 Cu, oxidation catalyst 07-P-19 Cu oxides in MCM-41 30-P-21 Cu 2+ reduction in Cu-ZSM-5 07-P-07 Cu/silica 1 l-P-20 Cu, UV-visible 15-P-11 Cu-zeolites
407
Cu-zeolites, oxidation catalysts 27-P-08 Cu, Zn mesoporous alumina 07-P-16 Cubic mesoporous silica, functionalized 07-0-02 CuI clusters in LTA 22-P-17 Cumene cracking 03-P- 14 04-P- 14 1 l-P-30 29-P-07 Cumene cracking on H-ZSM-5 28-P-16 Cumene, diffusion in MFI 19-O-03 Curcumin dye in MCM-41 22-P-21 CVD 11-P-24 CVD alkoxysilane 1 l-P-09 CVD alkoxysilane/MFI 10-P-09 11-O-02 CVD FeC13 11-O-05 CVD passivation 27-P- 17 CVOC abatement 30-0-05 Cycloalkane conversion 26-P- 10 Cyclobutylamine template 05-P- 19 Cyclohexane aromatisation 24-P-27 Cyclohexane isomerisation 26-P- 19 Cyclohexane oxidation 02-P-14 07-P-10 27-P-06 27-P-15 Cyclohexane, oxidation, total 30-P-09 Cyclohexane ring opening 26-0-03 Cyclohexanol, diffusion in ZSM-5 19-0-03 Cyclohexanone oxime 15-O-05 23-0-03 23-P-18 23-P-27 27-P-16 02-P-42 Cyclohexene aromatisation 24-P-22 Cyclohexene conversion 26-P- 17 29-P-29 Cyclohexene hydrogenation 2 l-P- 13 29-P-30 Cyclohexene oxidation 23-P-13 Cyclohex-2-en- 1-one condensation 26-P-16 Cyclopentane hydroconversion 23-P-17 Cytochrome C, adsorption 29-P-23 CZP zincophosphate
D D-AI-MCM-41 D-ZSM-5 1D confined system 2D correlation IR spectroscopy 2DNMR 13-P-18 13-P-19 DABCO-based template Dachiardite, AI ordering DC polarisation DCM resin/AIPO4-5 composites Deactivation, alkylation catalyst Deactivation, reforming catalyst Dealkylation, trimethylbenzene Dealuminated mordenite Dealuminated zeolite Y, Si/AI ratio Dealumination 05-P-14 11-P-25 12-P- 16 13-P-07 Dealumination, BEA 1 I-P-10 Dealumination, EMT
23-P- 15 23-P- 15 17-P- 17 12-O-01 13-P-24 02-P-27 0 l-P-07 22-0-04 21-O-04 24-P-06 24-P-23 25-P- 10 29-P-11 13-P-15 24-P-21 11-P-22 14-P-23
Dealumination, FAU 14-P-23 Dealumination, FAU, chemical 1 l-P-21 Dealumination, FAU, hydrothermal 1 l-P-21 Dealumination, FER 13-P- 17 Dealumination, MFI 29-P-06 29-P-26 Dealumination, MOR 12-P-05 Deboration 1 l-P- 16 n-Decane 26-P- 18 Decane conversion 13-0-02 n-Decane hydroconversion 26-P-06 29-P- 19 Decane, swelling agent 06-P-27 Deca(oxyethylene)oleyl ether, surfactant 08-0-02 Decomposition of water, photochemical 28-0-03 Defects, MFI 14-P- 19 Degradation, polyethylene 24-P-25 Degradation, polymers, catalytic 30-P- 17 Dehydration, Cd-FAU 09-P-06 Dehydration, clinoptilolite 11-P-26 Dehydration, isopropanol 29-P-06 Dehydration, K-LSX 09-0-01 Dehydration, MOR 09-P- 13 Dehydrocyclodimerisation, butadiene 22-0-03 Dehydrogenation, ethylbenzene 20-P-06 Dehydrogenation, methanol 10-P-05 Dehydroisomerisation, n-butane 24-0-01 Dehydroxylation, phenol 29-P-08 Delaminated zeolites 23-P-21 De novo simulation 16-P-09 DeNOx catalyst 30-P-29 DeNOx catalyst, aluminophosphate 30-P-31 DeNOx catalyst, Fe-zeolites 30-P-27 DeNOx catalyst, MCM-22 30-P- 13 DeNOx on Cu-MFI 16-P-20 DeNOx SCR ' 30-P- 10 DeNOx SCR by NH3 30-P-12 30-P-29 DeNOx SCR by CH4 10-O-01 30-P-I 5 30-P-22 30-P-28 30-P-35 DeNOx SCR by hydrocarbons 30-0-03 30-P-25 DeNOx SCR by propene 30-P-14 30-P-30 30-P-34 Densification, zeolite, thermal 10-P-07 Design of experiments (DOE) method 03-P- 16 Desulfurisation, modelling 15-P-22 Deuterium exchange 23-P- 15 Dewaxing 26-P-23 Dewaxing on Pt/AI-MCM-41 26-P-21 DFT (density functional theory) 15-P-11 DFT calculations 15-0-04 15-P-06 15-P-17 15-P-21 15-P-24 15-P-25 DFT calculations, alkene epoxidation 15-P- 18 DFT cluster calculations 15-O-03 15-P-11 15-P-13 15-P-20 15-P-22 DFT periodic calculations 15-0-03 Diagenetic zeolites 0 l-P-06 Diamond anvil cell 09-P-09 Diaromatics hydrodecyclisation 26-P- 13 Diatomite, coating by zeolites 21-P-07 Diazine adsorption, FAU 12-0-03
408
Dibenzothiophene adsorption 18-P-11 12-P-17 Dibenzothiophene hydrodesulfurisation Diblock copolymer surfactants 08-P-12 Dichloromethane degradation 30-0-05 Dielectric constant, zeolite films 20-P- 11 Dielectric spectroscopy 21-P-14 PL-4 Diesel pool 26-P-13 Diesel upgrading Diethylenetriamine template 02-P-41 Diffraction, anomalous 17-P-09 Diffraction, microcrystal 22-0-01 01-P-15 Diffuse reflectance, Ag 1I-P-20 30-P-21 Diffuse reflectance, Cu 04-P- 11 Diffuse reflectance, in situ Diffuse reflectance spectroscopy 07-P-14 15-P-11 26-P-14 26-P-22 Diffusion 16-P- 12 20-P-15 13-P-14 Diffusion, acetonitrile Diffusion, acetylene 19-P-07 19-0-02 Diffusion, aromatics Diffusion coefficients 19-P-08 20-P-15 Diffusion coefficients, reaction conditions 28-P-16 28-P-16 Diffusion constraints 19-0-04 Diffusion, effect of crystal morphology 19-K-01 Diffusion, hydrocarbons Diffusion, hydrocarbons, by 129XeNMR 19-P-09 19-P-09 Diffusion, MFI Diffusion, MFI, organics 19-0-03 19-P-10 19-P-08 Diffusion, MOR, n-hexane 20-P-15 Diffusion, PFG NMR 28-0-01 Diffusion, single file 20-P-15 Diffusivity, LTA coating 19-O-03 Diffusivity, MFI, organics 12-P-08 2,5-Dihydrofuran adsorption 24-P-29 Dimerisation, olefins 28-0-05 2,2-Dimethylbutane isomerisation 18-P-14 Dimethyldisulfide HDS 23-P-30 Diphenylmethane, chlorination 25-0-03 2,6-Dimethylnaphthalene 14-P-15 Dipole-dipole coupling 11-O-02 Disproportionation, aromatics 28-P-13 Disproportionation, cresols 29-P-19 Disproportionation, ethylbenzene Disproportionation, toluene 10-P-09 11-P-24 24-P-06 29-P-26 Dissolution, MFI 07-P-24 1l-P-30 DLH (double layered hydroxides), Fe,Co 30-P-26 n-Dodecane hydroisomerisation 08-P- 13 Dodecyl dimethyl benzylammonium surfactant 06-P-09 Dodecylamine, template 29-P-08 Dodecylphosphate surfactant 07-P-08 DON, see U T D - 1 Donor-acceptor interactions 22-P-06 Double bond isomerisation 23-P-26 Double-mesopore silica 06-P- 10 DRIFT spectroscopy 12-O-04 12-P-09
DRIFTS, in-situ 30-P-27 DRIFTS/PY 30-P- 18 Drinking water, deammoniation 3 l-P-09 Drug carriers 32-O-01 32-0-05 Drug carrier clinoptilolite 32-P-08 Drying, effect on ion exchange 1 I-P-20 Dual temperature ion exchange I l-P-18 Dubinin-Radushkevich equation 26-P-20 Dust, health effect 32-0-02 Dye molecules, encapsulation 21-O-02 22-P-06 Dyes in MCM-41 22-P-21 Dyes in mesoporous silica 22-P-20 Dyes, photochromic, encapsulated 22-P-07 Dyes in zeolites 22-P- 14 Dynamic pulse method 17-P-08 Dynamical processes, modelling 15-0-02
E-Caprolactam 23-P-27 Edingtonite from fly ash 18-P- 10 Edingtonite, lattice vibrations 16-P- i 9 EDS 09-P-10 Effect of H20 and SO2 on catalytic activity 30-P-22 Effluents, nitric oxide industry 30-P-34 Electric field gradient, FAU 14-P-27 Electrochemistry 20-P- 14 Electrode, anatase 22-P- 13 Electron density, SBA- 15 walls 08-0-03 Electron diffraction, HREM 14-P- 19 Electron-hole pairs, biphenyl/MFI 14-P- 18 Electron microscopy PL-5 Electron transfer in zeolite Ru-Y 28-0-03 Electron transfer, biphenyl/MFl 14-P- 18 Electronic materials 02-P-25 Electronic states 22-P- 17 EMT, acidity 13-P-21 14-P-23 EMT, transalkylation catalyst 25-0-04 EMT-MAZ overgrowth 02-P-06 Enantioselective catalysis 23-P-11 Enantioselective hydrogenation 23-P-25 Enantioselective synthesis, terminal epoxides 23-P-10 Encapsulation 07-P- 10 2 l-K-01 21 -O-05 22-P- 17 Encapsulation, AgI/LTA 14-0-04 Encapsulation, AgzS/LTA 27-P-14 Encapsulation, anthraquinone/BEA 11-O-01 Encapsulation, Au/FAU 24-P-29 Encapsulation, bipyridine/FAU 14-P-24 Encapsulation, bipyridine/MFI 22-P- 17 Encapsulation, CuI/LTA 21-0-02 Encapsulation, dyes 22-P-21 Encapsulation, dyes, MCM-41 02-P-14 Encapsulation, Fe complexes/FAU 10-O-03 Encapsulation, halides
409
23-P-19 HPA metal oxide photocatalysts 30-K-01 21-P-13 Mn complexes/FAU 21-P-11 Mn-bipyridyl/FAU 22-P- 18 PbI2/LTL 22-P-07 photochromic dyes 14-P-12 phthalocyanines 22-P-19 pigments Rb clusters, LTA 2 l-P-18 Tb[(CIBOEP)4P](acac)/MCM-41 22-P-09 14-P-07 ENDOR spectroscopy 31-P-10 Environment control Environmental catalysis 30-P-08 30-P-32 02-P-28 Epitaxial overgrowth CAN/SOD 02-P-28 Epitaxial overgrowth CHA/SOD 02-P-06 Epitaxial overgrowth MAZ/EMT 23-P-10 Epoxide, terminal, hydrolysis Epoxidation 2 l-P-07 27-P-06 29-P-30 Epoxidation, cyclohexene 24-P-14 Epoxidation, fixed bed Epoxidation, olefins 11-P-29 14-P-12 15-P-18 23-P-14 Epoxidation, alpha-pinene 24-P-14 27-0-02 Epoxidation, propylene 29-P-08 Epoxidation, styrene EPR spectroscopy 04-P- 10 04-P-I 1 05-P-I 1 13-P-08 13-P-09 14-O-05 14-P-12 14-P-20 14-P-37 15-P-11 30-P-26 14-P-15 EPR, cation impurities EPR, nitroxide 14-P-07 32-0-02 14-P-09 EPR, NO 14-P-18 EPR, polyaromatic ionisation 27-P-13 Erionite, Co 27-P-13 Erionite, Cu 27-P-13 Erionite, Fe 32-0-02 Erionite, health effect 27-P-13 Erionite, Ni 27-P-13 Erionite, oxidation catalyst 01-P-13 Erionite, in zeolitic tuff 29-0-01 ERS- 10 alkylation catalyst 29-O-01 ERS- 10, pore structure ESR (see EPR) 08-P-10 Esterification 28-P-14 Esterification, effect of hydrophobicity 28-P-11 ETBE 18-P-15 Ethanol adsorption 23-P-09 Ethanol conversion 27-P-14 Ethanol, in H2Oz synthesis 24-P-23 Ethanol, steam reforming 23-P-08 Ethanolamine, dehydration 18-P-12 Ethyl acetate adsorption 23-P-29 Ethyl acetoacetate condensation 29-0-01 Ethylbenzene 28-P-08 Ethylbenzene alkylation 20-P-06 Ethylbenzene dehydrogenation 29-P-19 Ethylbenzene disproportionation Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation, Encapsulation,
Ethylcyanoacetate-benzaldehyde condensation 23-0-04 Ethylene adsorption 12-P-09 Ethylene ammoxidation 10-P-08 Ethylene conversion 24-P- 10 Ethylene dimerisation 24-P-29 Ethylene glycol in sodalite cage 16-P-17 Ethylene polymerisation 24-0-05 24-P-17 Ethylenediamine template 05-P-08 09-P-08 Ethyleneimine, formation 23-P-08 ETS-4 11-P- 15 ETS-4, morphology 04-P- 16 ETS-4, synthesis 04-P- 16 ETS-4, Zr 04-P- 16 ETS- 10, acid site NMR 13-P-23 ETS-10, Bronsted acidity 24-P-15 ETS-10, Cr 27-P-15 ETS-10, Fe 27-P-15 ETS- 10, HRTEM PL-5 ETS- 10 modification 11-0-04 ETS- 10, oligomerisation catalyst 24-P- 15 p-Eugenol isomerisation 23-P-26 Europium cerium silicates 05-P- 12 EXAFS 01-O-03 11-O-05 13-P-32 14-P-39 21-O-03 23-0-05 EXAFS/XANES 07-P-13 29-P-25 Exhaust gas treatment 30-P-10 30-P-32 External sites, probing 13-P-25 External surface acidity 13-P-09 External surface properties 16-O-02 Extraframework AI, modelling 15-P-21 Extra-large pore zeolites PL-3
19F NMR 08-0-04 09-0-02 11-O-03 30-P-I 9 Factorial design 03-P- 13 FAPO (Fe-AIPO4) 2 l-P-07 FAPO, deNOx catalysts 30-P-31 FAPO-5 14-P-39 FAPO- 11 14-P-22 FAPO-18 14-P-39 Fatty acids, selective adsorption in MFI 23-P-20 Fatty oils, hydrogenation 23-P-20 FAU, see also LSX, LZ-210, SAPO-37, USY 13-P-21 FAU, acid sites 13-P-13 FAU, acid site NMR 13-P-23 FAU, acidic and basic 23-P-12 FAU, acidity 13-P-07 13-P-21 14-P-23 15-P-16 23-P-09 FAU, acidity, modelling 15-0-01 FAU adsorbent 12-O-03 16-O-03 16-P-14 18-P-07 18-P-11 18-P-15 FAU adsorbent, Ar/N2 17-P-15
410
FAU, adsorption 12-P-08 FAU, adsorption models 16-O-03 FAU, Ag 18-0-05 24-0-02 24-P- 19 FAU, A1 site in activated 13-P-18 FAU, alkylation catalyst 24-P-09 25-0-02 25-P-07 25-P-09 25-P-13 28-P-15 FAU, B-treated 11-P-23 FAU, Ba, adsorbent 16-O-03 FAU, Cd 09-P-06 FAU, Co 27-P-13 FAU, colloidal 02-0-03 02-P- 14 FAU, Cr exchange 3 l-P- 13 FAU cracking catalyst 11-P-23 FAU, crystallisation monitoring 02-P-37 FAU, Cs 29-P-20 FAU, Cs, Pt catalyst 23-0-05 FAU, Cu 12-P-09 17-P-14 27-P-13 FAU, Cu, oxidation catalyst 30-P-23 FAU, Cu, reforming catalyst 24-P-23 FAU, dealumination 1l-P-21 13-P-07 FAU, diffusion 19-P-07 FAU, diffusion, CH4-CF4, modelling 16-O-05 FAU drug carrier 32-0-05 FAU, effect of H20 on xylene adsorption 16-O-03 FAU, electric field gradient 14-P-27 FAU, Fe 27-P-13 30-P-I 1 FAU, Fe, HDS catalyst 12-P- 17 FAU, film synthesis 20-P-16 FAU, fluorination 11-P-I 7 FAU-Ga 10-P-06 FAU, H form 12-P-06 25-P-15 FAU, host 02-P-14 11-O-01 14-P-12 14-P-29 14-P-37 21-P-10 21-P-II 2 l-P- 13 22-P-07 23-P- 19 24-P-29 30-P-08 FAU, hydration 15-0-04 FAU hydration catalyst 23-P- 19 FAU hydrotreatment catalyst 26-P-08 FAU isomerisation catalyst 11-P-23 14-P-36 25-P-08 26-O-01 28-P-13 FAU, K, adsorbent 16-O-03 FAU, K-LSX, orthorhombic 09-O-01 FAU, La 13-P-13 FAU, La hydrogenation catalyst 26-0-03 FAU, La, proton sites 09-0-04 FAU, lattice vibrations 12-P-07 14-P-31 FAU, Li,Na, 23Na NMR 13-P-12 FAU, Li,Na, pyrrole adsorption 12-P-12 FAU/LTA mixture, from fly ash 18-P-10 FAU/LTL composites 07-P- 10 FAU membranes 20-0-02 FAU, mesopore imaging 14-0-01 FAU, mesoporous 1l-P-08 FAU, Mn 21-P-11 21-P-13 FAU, modelling 15-P-25 FAU, nanocrystals 02-P- 14 FAU, nanotubes formation on 22-P-08 FAU, Na 10-P-05 12-P-08 13-O-03 30-P-07
FAU, Ni 24-P-24 27-P- 13 FAU, Ni oligomerisation catalyst 24-P-17 24-P-24 FAU, Ni,W hydrocracking catalyst 1l-P-08 FAU, NiMo hydrotreatment catalyst 26-P-15 FAU, nitroxide EPR 14-P-07 FAU oxidation catalyst 27-P-13 FAU, P-treated 11-P-23 FAU, Pd/K,Na23-P-23 FAU, Pd, Heck catalyst 23-0-02 FAU, photocatalyst 30-P-20 FAU, phthalocyanine epoxidation catalyst 14-P-12 FAU, polymer degradation catalyst 30-P-17 26-P-20 FAU, porosity 16-0-04 FAU, proton tunnelling 17-P-08 FAU, Pt FAU, Pt aromatisation catalyst 15-P-09 FAU, Pt bifunctional catalyst 30-0-05 27-0-05 FAU, Pt-Pd hydrogenation catalysts 02-P-07 03-P-11 FAU, reagent 09-P-lO FAU, In-exchanged FAU, Ru bipyridyl photocatalyst 28-0-03 17-P-16 FAU, supercritical adsorption 16-0-02 FAU (111) surface simulation 02-0-03 FAU synthesis 03-P-15 FAU synthesis, microwaves 03-0-05 FAU synthesis, role of K and Na 13-P-16 FAU, toluene adsorption NMR 25-0-04 FAU, transalkylation catalyst 13-P-15 FAU, unit cell constant 29-P-23 FA U zincophosphate 17-P-14 FAU, Zn 26-0-01 FCC gasoline quality 26-0-05 FCC heavy gasoline, reforming Fe-AIPO4, s e e FAPO Fe-BEA 04-P-07 10-O-04 30-P-06 30-P-11 30-P-27 Fe in CIT-5, characterisation 16-P-09 FeCls, CVD 11-O-05 Fe,Co double layered hydroxides 30-P-26 Fe, coordination in FAPO-11 14-P-22 Fe distribution in MFI 13-O-02 Fe effect on citotoxicity 32-0-02 Fe-ERI, oxidation catalyst 27-P- 13 Fe-ETS-10 27-P-15 Fe, extra-lattice 30-0-02 Fe-FAU 30-P-11 Fe-FAU, HDS catalyst 12-P-17 Fe-FAU, oxidation catalyst 27-P- 13 Fe-FER 10-O-04 Fe-FER oxidation catalyst 29-P-25 Fe(III) impurities, zeolite Y 14-P- 15 Fe-LTL 07-P- 10 24-P- 11 Fe-MCM-22 14-P-21 Fe-MCM-41 06-P-28 07-P- 14 Fe-MCM-41 oxidation catalyst 29-P-25 Fe-MCM-41, redox behaviour 07-0-03 Fe-MEL oxidation catalyst 29-P-25
411
Fe-MFI
04-P-07 11-O-05 23-P-24 30-0-02 30-P-11 30-P-27 Fe in MFI, characterisation 12-O-02 16-P-09 Fe-MFI, deNOx catalyst 12-O-02 30-P-14 Fe-MFI oxidation catalyst 29-P-25 31-O-03 Fe-MFI, oxihalogenation catalyst 23-P-24 Fe-MFI, sulfide host 29-P-05 Fe-MFI synthesis 04-0-03 Fe-MFI synthesis, fluoride 04-P- 17 Fe-MOR 04-P-15 13-P-32 30-P-11 30-P-27 Fe-MOR, oxidation catalyst 27-P-13 Fe-MTW oxidation catalyst 29-P-25 Fe-MTW, synthesis 04-0-03 Fe203 nanoparticles in MCM-41 07-P-13 Fe, oxidation state in FAPO-11 14-P-22 Fe oxo binuclear species 11-O-05 Fe-phen complexes, encapsulated 02-P- 14 Fe Raney/MFI composite 30-P-29 Fe-SAPO-34 30-P-27 Fe sites, FAPO 14-P-39 Fe-TON 04-0-04 Fe-TON, synthesis 04-0-03 Fenton H202 chemistry 31-O-03 FER, acidity 13-P- 17 FER, adsorbent 17-P-06 FER, Ag 14-0-03 FER, AI distribution 13-P- 19 FER, Co 30-P-35 FER, Cu 14-0-03 FER, dealumination 13-P- 17 FER, Fe 10-0-04 FER, Fe oxidation catalyst 29-P-25 FER, isomerisation catalyst 24-P-21 26-O-01 26-P-09 FER synthesis 03-P-09 Ferrocene/MCM-41 07-P- 13 Ferromagnetic zeolites 22-P- 10 Fertilizers, zeoponic delivery 31-O-02 Fibers, health effect 32-0-02 Fibers, mesoporous silica PL-1 06-0-02 22-P-20 Fibers, MFI 2 l-P-06 Fibers, MFI, by bulk-material dissolution 02-P-26 Film, MFI/ceramic 20-P-09 Film, FAU 20-P-16 Film, LTA 20-P- 10 20-P- 15 20-P- 16 Film, LTA/glass 20-0-01 Film, MFI 20-0-04 Film, MFI on AI 20-P- 17 Film, MFI on cordierite 20-P- 13 Film, MFI on gold 20-P- 14 Film, zeolite, all-silica 20-P-11 Film, zeolite, anti-corrosion 22-0-04 Filtration media 21 -P-07 Filtration, MSU-X application 08-O-01 Fine chemicals 23-K-01 23-P-21 23-P-22 23-P-29 24-0-04 Fischer-Tropsch synthesis 24-P- 11
Fisheries, deammoniation 3 l-P- 12 Flexibility, zeolite lattice 13-P-22 Flue gas adsorption 18-P- 10 Flue gas, screening 18-0-01 Fuorescence 22-P-06 Fluorescence, dyes in mesoporous silica 22-P-20 Fluorescence, laser induced 13-P- 13 Fluoride anion effect 06-P-26 06-P-28 Fluoride in CoAPO synthesis 04-P-09 04-P- 17 Fluoride in MCM-41 synthesis 06-P-28 Fluoride in MFI synthesis 02-P-26 Fluoride in MOR synthesis 02-P-39 Fluoride, location in IFR 22-O-01 Fluorination of zeolite Y 1 l-P- 17 Fluorogallophosphate 11-O-03 16-P- 15 Fluorogermanates, layered 09-P- 12 Fly ash, source of silica 18-P- 10 Formation fields, M4 ls 06-P-25 FOS-5, synthesis and structure 09-0-03 Fractal, silica aggregates 14-P-25 Fragrance synthesis 23-P-22 Framework enumeration, zeolites 16-P- 13 Framework polarity 32-0-05 Framework substitution 04-P-07 Framework vibration, TS- 1 14-P-34 Framework vibrations, zeolites 12-P- 10 Freezing in confined systems 17-0-01 Frequency response 19-0-02 19-P-07 Friedel-Crafts alkylation 25-0-02 25-P-12 29-0-03 FSM from saponite 06-P- 15 FSM- 16 17-P-05 22-0-05 FSM- 16, AI, host 29-P-29 FTIR, BEA dealumination, realumination 11-P-22 FTIR, 2D correlation 12-O-01 FTIR, HPA 13-P-05 FTIR skeletal vibrations 13-P- 15 FTIR spectroscopy 09-0-04 1 I-P-21 12-O-03 12-O-04 12-P-06 12-P-09 12-P-13 12-P-15 12-P-16 13-O-02 13-O-04 13-P-09 13-P- 17 13-P-21 13-P-25 14-O-05 14-P-20 14-P-23 14-P-30 14-P-34 14-P-40 15-O-05 15-P-13 17-P- 11 22-P-21 26-P-22 27-0-05 29-P- 19 29-P-20 30-P-16 30-P-31 32-P-07 FTIR spectroscopy, in-situ 12-P- 14 23-P-23 FTIR-UV Vis 14-P- 12 Fuel cell catalyst 07-P-20 Fukui functions 15-P-06 Fukui function overlap method 15-P- 19 Fumed silica 02-P-35 Function groups 17-P-06 Functionalized mesoporous silica 07-0-02 Furan adsorption 12-P-08 Furfuryl alcohol, hydroxyethylation 23-P-06
412
G
H
Ga-BEA 03-P-10 Ga-CON 1 l-P- 16 Ga-DON 1 l-P- 16 Ga-FAU 10-P-06 Ga-MCM-22, activation 11-P-27 Ga-MCM-41 07-P- 14 Ga-MCM-58 29-P-19 Ga-MFI 03-P-10 Ga-MFI, activation 11-P-27 Ga-MTW 03-P-10 Gallophosphates 1 l-P- 12 Gallophosphates, activation 16-P- 15 Gallophosphates, phase change 11-O-03 Gallosilicate 05-P-07 GaPO-42 (LTA), stability 1l-P-12 Gas purification 18-P- 10 Gas sensors 2 l-P- 10 22-P- 11 Gas separation, CO2/C2 18-0-03 Gas separation, kinetic 18-0-03 Gases, structured 10-0-03 Gasoline pool PL-4 Gasoline quality, FCC 26-O-01 Gel composition 02-P-20 Gel composition, effect on synthesis 02-P-21 GeO2, FOS-5 structure 09-0-03 Germanates, fluoro, layered 09-P- 12 GIS beryllophosphate 05-P-06 GIS from fly ash 18-P-10 GIS manganese phosphate 05-P-11 Glass, controlled porosity 17-P- 12 Glass, porous, Beckmann catalyst 27-P-16 Glass support for LTA layer 20-0-01 Glass, volcanic, zeolitisation 0 I-P- 13 Glycerol carbonate 23-P-32 Glycidol synthesis 23-P-32 Glycol solvent 05-P-11 GME beryllophosphate 05-P-06 Gold 11-O-01 Gold support 20-P- 14 GON (see GUS-I) Grafted MCM-41 29-P-28 grafting 21-O-02 Grafting, aluminium 29-0-04 Grafting, mesoporous silicas 18-P-06 29-P-09 Grafting, one-step or two-step 29-P-31 Grains, porous catalysts 28-P- 12 Gravimetry, Ar/N2 adsorption 17-P- 15 Grazing incidence X-ray diffraction 20-0-04 Green chemistry 16-P-09 Grignard reagents 29-P-09 Growth surface, SSZ-24, AFM 02-0-05 Guanidine, supported catalysts 29-P- 10 GUS- 1 (GON) 02-P-27
IH 2D NMR 13-P-19 ~H-MAS NMR, acid sites 1 l-P-07 ~H MAS spin echo NMR 14-P- 10 IH-NMR 08-0-04 09-P-I 1 11-P-28 13-P-14 IH-NMR imaging 19-K-01 tH NMR, MFI synthesis 02-P-40 lH-27AIdipolar coupling NMR 13-P-23 IH(E7AI) TRAPDOR NMR 08-0-04 IH-29Si dipolar coupling NMR 13-P-23 2H-NMR 13-P-14 H2 adsorption, LSX 12-0-04 H-, Ce-, Fe-, Mo-, Cr-ZSM-5 23-P-24 H202 20-P-14 21-P-07 Hz02 conversion 27-P-11 H202, Fenton chemistry 31-O-03 H202, oxidation agent 27-0-01 27-P-09 27-P- 15 29-P-18 H~O2, in oxihalogenation 23-P-24 H202, photocatalytic synthesis 27-P-14 H3PO3 reactions 05-P-15 H2S effect 26-P-07 HAFS analysis 30-P-24 Haloaromatics olefination 23-0-02 Halogenide, K, in oxihalogenation 23-P-24 Hartree-Fock method 15-P-08 15-P-09 HDN (hydrodenitrogenation) 26-P-14 HDS catalysts 26-P-08 26-P-12 HDS, benzothiophene 26-P-07 HDS, dibenzothiophene 12-P-17 18-P-14 HDS, dimethyldisulfide HDS, thiophene 26-P- 17 26-P-22 Health, animals 32-P-06 32-P-I0 32-P- 11 Health, human 32-O-01 32-0-02 32-P-09 32-P-12 Heat storage 2 I-P-09 31-O-04 02-P-08 Heating rate Heavy metals 3 l-P-05 10-P-07 Heavy metal-exchanged zeolites 23-0-02 Heck olefination on Pd-zeolites 13-0-02 Heptane 26-P-18 n-Heptane 24-P-06 n-Heptane cracking 26-P-11 n-Heptane hydroconversion 18-P-10 Herschelite (CHA) from fly ash 13 -O-02 Heteroatom distribution 25-P-16 Heteropoly acid, alkylation catalyst 23-P-19 Heteropoly acids, encapsulated 13-P-05 Heteropoly acid microporous salts 09-P-09 HEU (see clinoptilolite) 01-P-10 Heulandite-type zeolites, Bulgaria 08-P-13 n-Hexadecane cracking 24-0-03 n-Hexadecane hydroconversion 26-P-21 n-Hexadecane hydroisomerisation 26-P-21 n-Hexadecane isomerisation 1 l-P-17 Hexafluoroethane reagent
413
Hexamethylbenzene, guest
14-P-29
1,6-Hexamethylenediamine, template
02-P-22 02-P-42 Hexamethyldisiloxane in pore modification 1l-P-09 n-Hexane aromatisation 15-P-09 28-0-02 n-Hexane conversion, silylated MFI 11-O-02 n-Hexane cracking 26-0-01 29-P-26 16-P-16 Hexane diamine template 19-K-01 n-Hexane diffusion, NMR imaging 19-P-08 n-Hexane diffusivity, MOR n-Hexane isomerisation 19-P-08 14-P-36 26-P-19 06-P-23 n-Hexane hydroisomerisation 24-P-24 Hexene formation 29-P-24 1-Hexene isomerisation 10-O-03 HgX2 encapsulated 25-0-02 4-Hydroxybutan-2-one reagent 17-P-07 High-silica zeolites 18-P-15 High-silica zeolite adsorbent 10-P-07 High temperature treatment 03-P-I2 High-throughput strategies 27-P-10 Histidine complexes, immobilized 02-P-25 HLS silica 25-P-11 HMS alkylation catalysts 06-P- 11 HMS, amine extraction 29-P-08 HMS catalysts 29-P-08 HMS, Co 28-P-07 HMS, Cr photocatalysts 29-P-08 HMS, Cu 29-P-31 HMS grafting HMS, Ti 23-P- 14 29-P-08 14-P-20 HMS, V 26-P-22 HMS, Zr, support 21-P-12 Hollow zeolite spheres 20-P-13 Honeycomb, cordierite 21 -O-03 Honeycomb, MCM-41 29-P-27 Honeycomb, MCM-48 14-P-16 Host-guest interaction HPA, s e e heteropoly acids 18-P-06 HPLC, mesoporous silicas for 14-P-19 HRSEM PL-5 14-P-19 HRTEM 01-P-15 HRTEM, Ag-clinoptilolite 32-0-03 Human byle 29-P-28 Hybrid acid catalyst 29-0-02 Hybrid MCM-41 08-P-10 Hybrid mesoporous acids 29-P-31 Hybrid organic-inorganic materials 22-0-02 Hybrid solids 13-P-20 15-P-17 Hydration, AIPO4 15-0-04 Hydration, FAU 23-P-19 Hydration, alpha-pinene 20-P-14 Hydrazine 17-P-07 19-0-02 Hydrocarbon adsorption 24-P-31 Hydrocarbons, C4, aromatisation 30-0-03 Hydrocarbons, chloro-, in SCR-NOx 11-O-02 Hydrocarbon conversion, silylated MFI Hydrocarbon diffusion, by 129XeNMR 19-P-09
Hydrocarbon pool, MTO Hydrocarbon removal Hydrocarbon removal, exhaust gases Hydroconversion, alkanes Hydroconversion, benzene Hydroconversion, cyclopentane Hydroconversion, n-decane Hydroconversion, n-heptane Hydroconversion methylcyclopentane Hydrocracking 1I-P-08 13-O-02 26-P-15 Hydrocracking, n-hexadecane Hydrodechlorination Hydrodecyclisation, aromatics Hydrodesulfurisation Hydrogel milling Hydrogen acceptor Hydrogen adsorption Hydrogen in refining Hydrogen transfer in ketone reduction Hydrogenation 26-P-08 26-P-13 Hydrogenation, acetonitrile Hydrogenation, asymmetric Hydrogenation, benzene Hydrogenation, CO Hydrogenation, CO2 Hydrogenation, crotonaldehyde Hydrogenation, cyclohexene Hydrogenation, cynnamaidehyde Hydrogenation, fatty oils Hydrogenation, liquid phase Hydrogenation, olefins Hydrogenation, rings Hydrogenation, toluene Hydrogenolysis, cyclohexene Hydroisomerisation, C5/C6 Hydroisomerisation, n-decane Hydroisomerisation, n-dodecane Hydroisomerisation, hexadecane 24-0-03 Hydroisomerisation, long-chain n-alkanes Hydrolysis, terminal epoxide Hydrophobic MCM-41 Hydrophobic zeolites Hydrophobic zeolite in epoxidation Hydrophobicity, BEA Hydrophobicity, MCM-41 Hydrophobicity, MCM-48 Hydrophobicity, mesoporous silica Hydrophobisation, clinoptilolite Hydrophobisation, mesoporous silica Hydroquinone Hydrotalcite, basic catalyst Hydrothermal natural zeolites Hydrothermal stability, MTS Hydrothermal transformation Hydrothermal transformation, clinoptilolite Hydrothermal treatment Hydrotreatment 26-P-08 26-P-12
24-P-18 3 l-P-07 30-P-32 16-0-01 26-P-15 26-P-16 29-P-19 26-P-11 11-O-01
26-P-18 24-0-03 23-P-16 26-P-13 18-P-14 02-P-09 25-0-05 17-P-10 PL-4 23-P-33 29-P-15 23-P-28 23-P-25 27-0-04 24-P-11 24-P-26 29-P-15 26-P-17 07-P-16 23-P-20 29-P-13 29-P-22 26-P-10 27-0-05 29-P-29 20-P- 18 26-P-06 08-P-13 26-P-21 26-P-23 23-P-10 17-P-13 19-P-06
11-P-29 28-P-14 29-0-02 06-P-06 06-P-27 32-0-04 29-P-09 27-P-17 23-0-05 0 l-P-06 06-P-07 02-P-36 32-P-07 11-P-25 26-P- 17
414
Hydrotreatment, mesoporous catalyst 26-P-14 Hydroxyalkylation of aromatics Hydroxyalkylation of furfuryl alcohol Hydroxyethylation with H-zeolites Hydroxyl groups, BEA Hydroxyl groups, silicalite Hydroxylation, aromatics Hydroxylation, phenol 07-P-07 Hydroxyls, bridging, NMR Hydroxysilane Hypothetical framework 07-P-21 Hypothetical framework, MCR- 16
IFR IFR, synthesis Imaging, ~H-NMR Immobilisation in FAU Immobilized base Immobilized enantioselective catalyst Immobilized Salen Co complexes Impact craters Impregnation 03-P-11 In exchange In-MFI ln-X ln-zeolites, deNOx catalysts Indium silicates, microporous Insertion compounds in porosil In-situ diffuse reflectance In-situ DRIFTS ln-situ IR spectroscopy 12-O-01 In-situ LTA synthesis ln-situ NMR In-situ ultrasound monitoring Interatomic potential technique Intercalation compounds Intercalation, MOR/magadiite Interfacial resistance, membrane Interference microscopy Internal reflection Iodide removal Ion dynamics Ionic conduction, lithium silicate Ionisation, polyaromatics IR spectroscopy, s e e FTIR Iran, natrolite Iran, natural zeolites Iridium zeolites, hydrogenation catalyst Isobutane alkylation Isobutane diffusion Isobutane in silicalite lsobutanol oxidation
26-P-22 23-P-21 23-P-06 23-P-06 28-P- 11 15-O-05 21 -P-07 27-P-17 14-P-10 29-P-08 16-P-13 16-P-07
22-0-01 03-0-04 19-K-01 24-P-29 23-0-04 23-P-11 23-P-10 0 l-P-06 10-P-05 09-P- 10 30-P- 15 09-P-10 10-O-01 05-P- 16 10-O-03 04-P-11 30-P-27 23-P-23 18-P-09 02-P- 18 02-P-37 16-O-02 22-P- 16 02-P-36 19-O-05 19-0-04 21-O-04 18-0-05 14-P-06 09-0-05 14-P- 18 0 l-P-08 3 l-P-06 26-0-04 24-P-20 19-0-04 16-P- 12 27-P- 13
Isobutene synthesis 24-0-01 Isobutyric aldehyde, formation 27-P- 13 Isodewaxing 26-P-23 Isodimorphism of templates 0 I-P- 11 Iso-eugenol 23-P-26 Isomerisation 13-0-02 26-P- 18 Isomerisation, 1-acetyl-2-metoxynaphthalene 25-P-08 Isomerisation, alkanes 26-0-02 Isomerisation, n-butane 24-P- 16 29-P- 17 Isomerisation, butenes 24-P-21 Isomerisation, n-butene, skeletal 14-P-22 Isomerisation, C6 hydrocarbons 26-P- 19 Isomerisation catalyst, treated USY 11-P-23 lsomerisation, cresols 28-P- 13 lsomerisation, cyclohexene 24-P-22 Isomerisation, 2,2-dimethylbutane 28-0-05 Isomerisation, p-eugenol 23-P-26 Isomerisation, n-hexane 14-P-36 19-P-08 26-O-01 Isomerisation, 1-hexene 29-P-24 Isomerisation, light paraffins 06-P-23 Isomerisation, long-chain n-alkanes 26-P-23 Isomerisation, olefins 26-P-09 Isomerisation, toluene, modelling 15-P-20 lsomerisation, xylenes 12-P- 14 28-P-06 Isomerisation, xylenes, modelling 15-P-20 Isomerisation, xylene, NMR 12-0-01 lsomorphous substitution, B 11 -P- 16 13-P- 11 Isomorphous substitution, A! 1 I-P-16 lsomorphous substitution, AIPO4 30-P-31 lsomorphous substitution, AIPO4-31 14-P- 13 lsomorphous substitution, Co 04-P-II 04-P-13 04-P-18 Isomorphous substitution, Cr 04-P-08 lsomorphous substitution, Fe 04-0-03 04-0-04 04-P-17 Isomorphous substitution, Fe/MCM-41 07-0-03 Isomorphous substitution, Ga 1 I-P-16 11-P-27 Isomorphous substitution, MCM-41 29-P- 18 Isomorphous substitution, MFI 13-O-02 Isomorphous substitution, Nb 0 l-P- 14 Isomorphous substitution, Ta 01 -P- 14 Isomorphous substitution, V 14-P-33 24-P-07 Isomorphous substitution, Zn 04-P- 14 Isomorphous substitution, Zr 04-P- 16 Isopropanol adsorption 18-P- 15 Isopropanol dehydration 29-P-06 Isopropylation 25-P-09 25-P-16 Isopropylation, biphenyl 16-P-08 29-P-11 Isopropylation, naphthalene 25-P-06 lsopropylnaphthalene 25-P- 16 Isosteric heats of adsorption 17-P- 14 Isotherm of adsorption 17-P- 15 Isotopic labelling, MTO 24-P- 18 Isotopic traces technique 23-P- 15 IST- 1 02-P-33 IST-2 02-P-33
415
ISV (see ITQ-7) ITQ-2 acidity ITQ-2, fine chemistry catalyst ITQ-4 (IFR) ITQ-6, fine chemistry catalyst ITQ-7, alkylation catalyst
13-0-04 23-P-21 22-0-01 23-P-21 24-P-20
Jet-loop reactor Jordanian CHA-PHI tuff
28-P- 16 31-O-01
K
39KNMR K exchange K cation in synthesis K-FAU K-FAU, adsorbent K+ location, LSX K-LTL, catalyst K-M (see MER) K, Sr-KFI, synthesis Kanemite-derived mesoporous silica Ketones, unsatutated Keywords Kinetic modelling, NO-N20 interaction KIT-I Knight shift Knoevenagel condensation 04-0-02 23-0-04 23-P-29 Kr adsorption, AEL KSW-2, HRTEM KZ-2 (TON), synthesis
La exchange La in AIPO4, deNOx catalyst La-FAU 09-0-04 La-FAU ring opening catalyst La-MCM-4 l, stability La promoters, deNOx Lactame Lake fresh water zeolitization Lamellar aluminophosphate Large crystals activation Large crystals, MFI Large pore Ni(II) phosphate VSB-1 Large pore vanadosilicates Large pore zeolites PL-3 17-P-07 Large pore zeolite catalysts 25-P-06 25-P-10 26-P-15 26-P-16
09-0-01 1l-P- 18 03-0-05 09-0-01 16-0-03 09-0-01 23-P-30 02-P-21 PL-1 23-P-33 PL- 1 16-P-20 25-P-16 14-P-37 29-P-23 17-O-03 PL- 1 04-0-04
1 l-P-19
30-P-31 13-P-13 26-0-03 06-P-19 30-P-25 23-P-21 01-P-10 02-P- 11 14-P-38 02-P-15 22-0-03 04-0-05 24-P-06 28-P-13
Laser ablation 14-P-29 Laser dyes, mesoporous silica 22-P-20 Laser-induced fluorescence 13-P-13 Lattice dynamical calculations 16-P-19 Lattice energy calculation 07-P-21 Lattice model, adsorption 16-P-10 Lattice vibrations 12-P-07 14-P-31 16-P-18 Lattice vibrations, natrolite 16-P-19 Laumontite, cation exchange 31-P-12 Layer-by-layer shaping method 2 l-P-06 Layered compounds 02-P- 11 Layered Cu molybdate 09-P-07 Layered double hydroxide, Fe,Co 30-P-26 Layered germanates 09-P-12 Layered silicate 02-P-25 02-P-36 Layered zeolite menbranes 20-0-02 LCO, reforming 26-0-05 Leaching, MFI 07-P-24 Lead removal 3 I-P-06 Lewis acid 14-P-21 29-0-03 Lewis acid sites 13-P-08 13-P-17 Lewis acidity 13-P-19 Lewis basic sites 15-P-22 7Li'MAS NMR 09-0-05 7Li NMR, FAU adsorbent 12-P-12 Li exchange 01-0-04 Li,Na-FAU, 23Na NMR 13-P-12 Li,Na-FAU, pyrrole adsorption 12-P-12 Li-LSX 12-O-04 Li-LTA, H2 adsorbent 17-P-10 Li-Phillipsite 01-O-04 Li silicate RUB-29 09-0-05 Linde F (see EDI) Linkers, covalent, LTA/glass 20-O-01 Liquid crystals, confined 21-P-14 Liquid phase sulfoxidation 27-P-09 Low silica zeolites, synthesis 05-P-07 LSX (low-silica X, FAU), JTo NMR 14-0-02 LSX, alkali-exchanged 14-0-02 LSX, K 09-0-01 LSX, La 09-0-04 12-0-04 LSX, Li 12-0-04 LSX, Na LTA adsorbent 18-O-03 18-P-07 17-P-15 LTA adsorbent, Ar/N2 17-P-16 LTA, adsorption, supercritical 14-0-04 LTA, Ag 18-P-09 LTA, capillary column 23-P-32 LTA, catalyst 14-P-06 LTA, cation relaxation 02-P-37 LTA, crystallisation monitoring 19-P-07 LTA, diffusion 15-P-08 LTA, encapsulation modelling 18-P-10 LTA/FAU mixture, from fly ash 20-0-01 LTA, film, glass supported LTA, film 20-P-10 20-P-16 1 l-P-12 LTA, GaPO
416
LTA, Hz adsorbent 17-P- 10 LTA host 14-0-04 2 l-P- 18 22-P- 17 LTA, host, sulfides 22-P- 19 LTA, Li 17-P- 10 LTA, membranes 20-0-02 LTA, Na 10-P-05 30-P-07 LTA, nanotubes formation on 22-P-08 LTA reagent 03-P-11 LTA, synthesis 02-P-18 02-P-29 02-P-32 LTA, synthesis, in-situ 18-P-09 LTA, synthesis, role of K and Na 03-0-05 LTA, ~70 NMR 14-0-02 LTA, P occlusion 18-P- 13 LTA, polystyrene beads 2 I-P- 12 LTA, reagent 02-P-07 LTL host, Pbl2 clusters 22-P-18 LTL synthesis 02-P- 19 LTL synthesis, alkaline earth effect 02-P-17 LTL, acid site NMR 13-P-23 LTL/FAU composites 07-P- 10 LTL, Fe 07-P-10 24-P-11 LTL, formation of nanotubes on 22-P-08 LTL, K, catalyst 23-P-30 LTL, lattice vibrations 12-P-07 LTL, morphology 02-P- 17 LTL, Pd, Heck catalyst 23-0-02 LTL, Pt aromatisation catalyst 15-P-09 LTL, Pt/K catalyst 1 l-P-07 Luminescence spectroscopy 22-P-09 27-P-11 Luminescence, Ag-LTA 14-0-04 Luminescence, PbljLTL 22-P- 18 LZ-210 (FAU) 18-O-05
M M41 s synthesis 07-P-24 M41 s, XRD 06-P-05 Macrocycles, aza05-0-03 Macrocycle synthesis 28-0-04 Macroporosity, BEA 2 l-P- 15 Magadiite-intercalated MCM-22 05-P- 14 Magadiite in MOR synthesis 02-P-36 Magadiite, pillared 23-P- 18 Magnetic properties 2 l-P- 18 22-P- 10 Magnetic semiconductors, diluted 21-O-03 Magnetic susceptibility 11-O-05 Magnetism, Rb clusters in LTA 21-P-I 8 Magnetite, guest 22-P- 10 Manganese complexes in FAU 2 l-P-13 Manganese phosphate, Al-substituted 05-P-11 Manometry, high-resolution 17-P- 15 MAPSO-31, Pt catalyst 26-P-06 MAPSO-56 (Co,Mn,Zr) 05-P- 18 Market, gasoline PL-4 Market, zeolite PL-4
MAS-5 06-P-07 MAS NMR (see individual nuclei) MAS NMR, high temperature 14-P- 17 Mass spectrometry 14-P-29 MAZ-EMT overgrowth 02-P-06 MBIK (methyl isobutyl ketone) synthesis 23-0-05 MCM-22, see MWW MCM-36, basicity 10-0-02 MCM-41 06-P-07 08-P-06 17-P-17 25-P-13 27-P-09 MCM-41, adsorbent 17-0-01 MCM-41 adsorbent, VOC removal 18-P- 12 MCM-41, adsorption 17-P- 12 MCM-41, fine chemistry catalyst 23-P-21 MCM-41, ZTAI-NMR 06-P- 17 MCM-41 alumination 23-P-33 25-P-12 MCM-41, aluminosilicate 06-P-08 MCM-41 Beckmann catalyst 23-0-03 MCM-41 bifunctional catalyst 26-P- 18 MCM-41 catalysts 28-0-04 MCM-41, Ce 07-P-23 MCM-41, Cu 07-0-04 MCM-41, deuterated 23-P- 15 MCM-41, Fe 06-P-28 07-0-03 07-P- 13 07-P-14 MCM-41, Fe oxidation catalyst 29-P-25 MCM-41, functionalized, synthesis 07-0-02 MCM-41, Ga 07-P- 14 MCM-41, grafting 17-P- 13 29-P-28 29-P-31 MCM-41, honeycomb 21-O-03 MCM-41, host 07-P- 19 21-O-05 21-P-14 22-P-09 22-P-21 22-P-08 MCM-41 hydrogenation catalyst 23-P-28 MCM-41 hydrophobisation 29-0-02 29-P-09 MCM-41 hydrotreatment catalyst 26-P-14 26-P-17 MCM-41 in HPLC 18-P-06 MCM-41 isomerisation catalyst 24-P-22 MCM-41, Mn, DeNOx catalyst 30-P- 12 MCM-41, Nb 07-0-04 24-P-12 MCM-41, Ni, hydrodechlorination catalyst 23-P-16 MCM-41, Ni,Zr 23-P-28 MCM-41, noble metals 29-P-22 MCM-41, porosity by positron annihilation 12-P-I 1 MCM-41, Pt chiral hydrogenation catalyst 23-P-25 MCM-41, Pt hydroisomerisation catalyst 26-P-21 MCM-41, reagent 07-P- 10 MCM-41 silylation 29-0-02 MCM-41, size control 06-P-09 MCM-41, spheres 06-P- 13 MCM-41, stability, effect of AI 06-P- 19 MCM-41, stability, effect of Ce 06-P- 19 MCM-41, stability, effect of La 06-P-19 MCM-41 support 24-0-05 26-P-07 26-P-12 27-P-10 29-P-22 MCM-41 support, chiral catalyst 23-P-10 23-P-11 MCM-41, synthesis 06-O-01 06-P-14 06-P-26 07-P-24 MCM-41, synthesis, aging effect 06-P-21
417
MCM-41, synthesis, microwave 03-P- 15 MCM-41, synthesis, secondary 06-P- 10 MCM-41, Ti 07-P- 14 22-P-06 24-P- 12 29-P-30 29-P-18 MCM-41, Ti, oxidation catalyst 29-P-21 MCM-41, transition metals 29-P-18 MCM-41, V, oxidation catalyst 08-P-14 MCM-41, wall properties 06-P-28 MCM-41, washing effect 06-P-05 MCM-41, XRD 29-P-24 MCM-41, Zr, isomerisation catalyst 29-P-18 MCM-41, Zr, oxidation catalyst 17-P-12 MCM-48, adsorption 29-0-04 MCM-48, alumination 23-0-03 MCM-48, Beckmann catalyst 06-P-12 MCM-48, Cr 29-P-27 MCM-48, honeycombs PL-5 MCM-48, HRTEM 06-P-06 MCM-48, hydrophobicity 29-P-27 MCM-48, morphology 06-P-06 MCM-48, stability 06-0-04 06-P-06 MCM-48, swelling 06-O-01 06-P-24 07-P-06 MCM-48, synthesis 29-P-30 MCM-48, Ti 06-P-06 07-P-06 MCM-48, V MCM-48, ~29XeNMR 06-P- 16 29-P-19 MCM-58 16-P-07 MCR- 16, hypothetical structure 29-P-25 MEL, Fe oxidation catalyst 14-P-08 MEL, Mo 14-P-20 MEL, V 17-0-01 Melting in confined systems 23-P-10 Membrane, asymmetric separation 20-P- 18 Membrane, BEA/alumina 20-P-12 Membrane, BEA/ceramic 20-P-18 Membrane, catalytic reactor 28-0-03 Membrane, FAU Membrane, MFI 03-P- 17 20-P-06 20-P- 17 Membrane, MFI/alumina 20-O-05 Membrane, MFI/ceramic 20-P- 12 Membrane, MOR 20-0-03 Membrane, MOR/alumina 20-P- 18 Membrane, VOC removal 20-P-12 Membrane, zeolites 20-0-02 20-P-07 Membrane, zeolite, modelling 16-O-05 Membrane, zeolite/polymer 19-0-05 Membrane, zeolitic, supported 20-0-03 Memory effect PL-2 Menthene condensation 23-P-29 MER from fly ash 18-P-10 Mercapto functionalisation 07-P- 17 Mesophases 08-P-12 Mesopores, FAU 1 l-P-08 14-0-01 Mesopores, MFI 03-0-02 1l-P-30 26-0-02 Mesoporosity SBA-15 08-0-03 08-0-04 Mesoporous alumina 07-P-08 07-P- 18 Mesoporous alumina, Cu, Zn 07-P- 16
Mesoporous aluminosilicate 06-P-07 06-P-08 06-P-22 Mesoporous anatase 22-P- 13 Mesoporous basic catalysts 29-P- 10 Mesoporous carbon PL- 1 07-0-01 07-P-22 29-P- 13 Mesoporous-microporous mixed structures 06-0-03 Mesoporous molecular sieve, keywords PL-1 Mesoporous molecular sieves 17-O-01 17-P-05 29-P-30 Mesoporous silica (see also specific names, e.g. FSM-16, HMS, KIT-l, KSW-2, LMV-1, M41s, MAS-5, MCM-41, MCM-48, MSU-X, MTS, SBA-n) PL-1 06-P-07 06-P-20 07-P-24 08-P-05 08-P-06 08-P-07 17-P-17 25-P-13 27-P-09 29-P-30 Mesoporous silica, acidity 29-0-03 Mesoporous silica, activation 29-P- 16 Mesoporous silica, 27AI_NMR 06-P- 17 Mesoporous silica adsorbent 17-0-01 17-P-05 17-P-12 18-P-12 23-P-17 28-P-10 Mesoporous silica adsorbent, VOC removal 18-P-12 Mesoporous silicas, adsorption 17-P- 12 Mesoporous silica alumination 23-P-33 25-P-12 29-0-04 Mesoporous silica alkylation catalyst 25-P-11 Mesoporous silica, Beckmann catalyst 23-0-03 Mesoporous silica, bifunctional catalyst 26-P-18 Mesoporous silica, Ce 07-P-23 Mesoporous silica, Co 08-0-02 29-P-08 Mesoporous silica, Cr 06-P- 12 Mesoporous silica, Cr photocatalysts 28-P-07 Mesoporous silica, cracking catalyst 08-P- 13 Mesoporous silica, Cu 07-0-04 29-P-08 Mesoporous silica, Fe 06-P-28 07-0-03 07-P-13 07-P-14 29-P-25 Mesoporous silica, Fe oxidation catalyst 29-P-25 Mesoporous silica fibers 06-0-02 22-P-20 Mesoporous silica, fine chemistry catalyst 23-P-21 Mesoporous silica, functionalized 07-0-02 07-P-17 08-P-08 08-P-I 0 29-P-16 Mesoporous silica, Ga 07-P- 14 Mesoporous silica, grafting 17-P-I 3 29-P-28 29-P-31 Mesoporous silica, honeycomb 21-O-03 29-P-27 Mesoporous silica, host 07-P- 19 21-O-05 21 -P- 14 22-P-09 22-P-21 22-P-08 29-P-17 22-P-20 29-P-29 Mesoporous silica, HPA support 25-P-16 Mesoporous silica in HPLC 08-O-01 18-P-06 Mesoporous silica, HRTEM PL-1 PL-5 Mesoporous silica, hybrid acids 08-P-10 Mesoporous silica, hydrodechlorination catalyst 23-P-16 Mesoporous silica hydrogenation catalyst 23-P-28 Mesoporous silica, hydrogenation catalyst, chiral 23-P-25
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Mesoporous silica, hydroisomerisation catalyst 08-P- 13 26-P-21 Mesoporous silica, hydrophobicity 06-P-06 Mesoporous silica hydrophobisation 29-0-02 29-P-09 Mesoporous silica, hydrotreatment catalyst 26-P-14 26-P-22 Mesoporous silica, isomerisation catalyst 24-P-22 29-P-24 Mesoporous silica from kanemite PL-1 Mesoporous silica, Ni 08-0-02 Mesoporous silica, Mn, DeNOx catalyst 30-P-12 Mesoporous silica, Mo 14-P-26 Mesoporous silica, morphology 29-P-27 Mesoporous silica, Nb 07-0-04 24-P-12 Mesoporous silica, Ni 23-P- 16 Mesoporous silica, Ni,Zr 23-P-28 Mesoporous silica, noble metals 29-P-22 Mesoporous silica, oxidation catalyst 29-P- 18 Mesoporous silica, photocatalyst 24-P-07 24-P-12 Mesoporous silica, polymer degradation catalyst 24-P- 13 24-P-25 Mesoporous silica, porosity 08-0-03 Mesoporous silica, redox catalyst 23-P- 14 Mesoporous silica from saponite 06-P-15 Mesoporous silica spheres 06-0-02 06-P-13 Mesoporous silica spheres, SBA- 15 08-P-07 Mesoporous silicas, stability 06-O-01 Mesoporous silica silylation 29-0-02 Mesoporous silica, size control 06-P-09 Mesoporous silica, spheres 06-P-13 Mesoporous silica, stability 06-P-06 06-P- 19 08-P- 13 Mesoporous silica support 24-0-05 26-P-07 26-P-12 27-P-10 29-P-22 Mesoporous silica support, chiral catalyst 23-P- 10 23-P- 11 Mesoporous silica, swelling 06-0-04 06-P-06 Mesoporous silica, synthesis 06-0-01 06-P-14 06-P- 18 06-P-21 06-P-22 06-P-24 06-P-25 06-P-26 06-P-28 07-P-06 07-P-24 08-0-02 08-P-09 08-P-11 08-P-12 Mesoporous silica, synthesis, acidic pH 06-P-28 29-P-16 Mesoporous silica, synthesis, aging effect 06-P-21 Mesoporous silica, synthesis, microwave 03-P-15 Mesoporous silica synthesis, pH effect 06-P-20 Mesoporous silica, synthesis, secondary 06-P-10 Mesoporous silica, template extraction 06-P-11 Mesoporous silica, texture 08-P- 14 Mesoporous silica, Ti 07-P-14 22-P-06 23-P-14 24-P-12 29-P-08 29-P-18 29-P-30 Mesoporous silica, transformation 06-P- 18 Mesoporous silica, transition metals 29-P-21 Mesoporous silica, V 06-P-06 07-P-06 14-P-20 24-P-07 29-P-18 Mesoporous silica, XRD 06-P-05
Mesoporous silica, wall properties 08-P- 14 Mesoporous silica, washing effect 06-P-28 Mesoporous silica, 129XeNMR 06-P- 16 Mesoporous silica, Zr 26-P-22 29-P-18 29-P-24 Mesoporous single crystals 07-P-15 Mesoporous sulfides 1 I-P-11 Mesoporous titania 07-0-05 07-P-12 Mesoporous zirconia 07-P- 11 Mesoporous zirconia fuel cell catalyst 07-P-20 Mesostructural transformation 06-P-26 04-P-11 05-0-03 Metal aluminophosphates 32-P-07 Metal cations 04-0-01 Metal cation reduction 05-0-03 Metal cations in MeAPO synthesis 22-0-04 Metal corrosion prevention 24-0-05 24-P-08 Metallocene, supported catalyst 27-P-06 Metallosilicates, microporous 29-P-20 Methanol adsorption 11-P-25 Methanol amination 07-P- 19 29-P-20 Methanol conversion 10-P-05 Methanol dehydrogenation 24-P- 12 24-P-26 Methanol formation Methanol in alkylation 15-0-03 25-0-03 25-P- 13 Methanol to hydrocarbons 24-P-18 Methanol, reagent 25-0-01 Methanol, steam reforming 24-P-23 Methylamine in MFI synthesis 04-O-01 N-Methylation, aniline 25-P-11 Methylation, 4-methylbiphenyl 25-0-01 Methylation, toluene, model 15-0-03 4-methylbiphenyl, methylation 25-0-01 Methylcyclohexane cracking 26-P-11 Methylcyclopentane hydroconversion 1 I-O-01 Methylene silanes 2 I-P- 16 N-Methyl hexahydrojulodinium template 02-P-30 Methylnaphtalene alkylation 25-P- 13 Methyloxirane ring opening 23-P- 15 Methylpropyl ether 27-0-02 MFI 02-P-31 12-P-13 14-O-03 16-P-06 23-P-06 30-P-18 MFI, acid site NMR 13-P-23 MFI, acidity 13-P-08 13-P-25 MFI, acidity, modelling 15-0-01 MFI adsorbent 17-O-02 18-P-07 18-P-08 18-P-15 19-O-02 MFI, adsorption, biphenyl 14-P- 18 MFI, adsorption, bipyridine 14-P-24 MFI, adsorption, chloroalkenes 17-P- 11 MFI, adsorption modelling 16-P- 10 16-P- 12 MFI, Ag 14-O-03 15-P-10 30-0-03 30-P-28 MFI, Ag, deNOx catalyst 30-P-34 MFI, Ag, photocatalyst 30-P- 16 MFI, AI in activated 13-P- 18 MFI, A! distribution 13-P- 19 MFI, alkali leaching 07-P-24 1 l-P-30 MFI alkane conversion catalyst 15-P- 15
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MFI alkylation catalyst 25-O-01 25-0-05 25-P-09 28-P-15 MFl/alumina membranes 20-0-05 MFI aromatisation catalyst 28-0-02 MFI, Beckmann catalyst 15-0-05 27-P- 16 MFI catalyst 24-P- 10 26-P- 10 MFI, Ce, oxihalogenation catalyst 23-P-24 MFI/ceramic composite membrane 20-P- 12 MFI, Co 10-P-08 04-P- 18 30-0-03 MFI, Co, deNOx catalyst 30-P-34 MFI, coke-selectivated 28-P-06 MFI on cordierite 30-P-33 MFI, crystal size control 02-P- 15 MFI cracking catalyst 28-P- 16 MFI, Cr, oxihalogenation catalyst 23-P-24 MFI, Cs 29-P-20 MFI, Cu 04-0-01 12-P- 15 14-O-03 15-P-13 30-0-03 30-P-09 30-P-33 MFI, Cu, aromatisation catalyst 24-P-30 MFI, Cu, deNOx catalyst 16-P-20 30-P- 14 MFI, Cu oxidation catalyst 27-P-12 MFI, Cu, synthesis 14-P-40 MFI, dealuminated, acidity 29-P-06 MFI dealumination 29-P-26 MFI, defects 14-P- 19 MFI, deNOx catalyst 30-P-13 30-P-25 MFI, deuterated 23-P- 15 MFI, diffusion 19-0-04 19-P-09 19-P- 10 MFI, diffusion, hydrocarbon 19-K-01 MFI, electronic material 14-P- 18 MFI, enhanced acidity 13-P- 10 MFI, Fe 04-P-07 11-O-05 12-O-02 16-P-09 30-P-11 30-P-27 31-O-03 MFI, Fe, deNOx catalyst 30-P-14 MFI, Fe oxidation catalyst 29-P-25 MFI, Fe, oxihalogenation catalyst 23-P-24 MFI, Fe, sulfide host 22-P-19 MFI, Fe, synthesis 04-0-03 MFI, Fe, synthesis, fluoride 04-P- 17 MFI fibers 2 l-P-06 MFI film 20-0-04 MFI film on AI support 20-P-17 MFI film on ceramic 20-P-09 MFI film on gold 20-P-14 MFI, Ga 03-P- 10 MFI, Ga, activation 11-P-27 MFI, growth rate 02-P-08 MFI, heteroatom location 13-O-02 MFI, hierarchically mesostructured 06-0-03 MFI host 13-P-06 14-P-29 15-P-26 2 l-P- 10 MFI, indium 30-P- 15 MFI, In deNOx catalyst 10-O-01 MFI isomerisation catalyst 12-O-01 25-P-08 26-0-01 MFI, large crystals activation 14-P-38 MFI, lattice vibrations 12-P-07 MFI, macropores 19-0-03
MFI membrane 03-P-17 19-O-05 20-0-02 20-P-06 MFI, mesoporous 03-0-02 1 l-P-30 26-0-02 MFI, Mo 14-P-08 30-K-01 MFI, Mo, oxihalogenation catalyst 23-P-24 MFI, modelling 15-P-06 15-P-25 MFI, nanoparticles agglomeration 03-P- 14 MFI, Na form 30-P-07 MFI, Na synthesis 02-P-09 MFI nanoslabs 02-0-04 MFI, nanotubes formation on 22-P-08 MFI, Ni 04-P-06 23-P-20 MFI, Ni deNOx catalyst 30-P-30 MFI nucleation 02-0-02 MFI, organozeolite 2 I-P- 16 MFI, oxihalogenation catalyst 23-P-24 MFI photocatalyst 15-P-07 30-K-01 30-P-20 MFI, polycrystalline film on cordierite 20-P-13 MFI, pore mouth plugging 11-O-02 MFI, pore mouthing 11-P-24 MFI porosity 26-P-20 MFI, Pt 17-P-08 23-P-20 MFI/Raney composite catalyst 30-P-29 MFI-resin composite 03-P-07 MFI, silylated 19-0-03 MFI, silylated, hydrocarbon conversion 11-O-02 MFI, silylation 10-P-09 11-O-02 MFI sites modelling 15-P-24 MFI, solid state synthesis 04-P-06 MFI, supercritical adsorption 17-P- 16 MFI spheres 03-P-07 21-P-06 MFI synthesis 02-O-01 02-P-31 02-P-41 MFI synthesis, bulk-material dissolution 02-P-26 MFI synthesis, clear solution 02-0-04 02-P-I 6 MFI, synthesis, microwave 03-P- 15 MFI synthesis, phosphate-affected 02-P-40 MFI, synthesis precursors 02-O-01 MFI, template removal 13-P- 10 MFI, thermal treatment 14-P-38 MFI, Ti (see TS-1) 14-P-20 MFI, V 24-P-27 MFI, Zn 24-P-30 24-P-31 MFI, Zn, aromatisation catalyst 28-0-02 MFI, Zn,Ni 24-P-31 MFI, Zn,Ni aromatisation catalyst 29-P-05 MFI, Zn, sulfide host 04-P-14 MFI, Zn, synthesis 02-P-17 Mg in alkaline synthesis 23-P-13 Michael condensation 19-P-08 Microbalance, oscillating 31-P-15 Microbial oxidation 01-P-15 Microbicide 13-P-07 Microcalorimetry Microcalorimetry, adsorption 17-0-02 17-0-03 17-P- 16 Microcalorimetry, Ar/N2 adsorption 17-P- 15 Microcalorimetry, chloroalkene adsorption 17-P-11 Microlaser, potential 21-O-04
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Microporosity SBA- 15 08-O-03 08-0-04 Microporous-mesoporous mixed structures 06-0-03 Microscopy, atomic force, s e e AFM Microscopy, electron PL-5 Microscopy, interference 19-0-04 Microwave heating 20-P-38 Microwave heating, zeolites 1 l-P- 13 Microwave in catalysis 28-0-02 Microwave in synthesis 03-P- 15 MIL-34 AIPO4 05-P- 19 Milk yield, cows 32-P- 10 Miocene 01-O-02 Mn(x)Cd(l-x)S 21-O-03 MnAPO-31 14-P- 13 MnAPO-34 29-P- 14 MnAPO-43 05-P- 11 Mn-Bipyridyl, encapsulated 2 l-P- 11 Mn-FAU 21-P-11 21-P-13 Mn-MCM-41, deNOx catalyst 30-P- 12 Mn-zeolites, NOx storage 30-0-04 Mo-BEA 14-P-08 Mo incorporation in SBA-1 and-3 14-P-26 Mo-MEL 14-P-08 Mo-MFI 14-P-08 23-P-24 30-K-01 Mo-MFI, oxyhalogenation catalyst 23-P-24 Mo,Zr-MCM-41 26-P-22 Mobility, adsorbed molecules 16-O-03 Modelling, adsorption 12-0-03 16-P-06 18-P- 15 19-0-02 Modelling, adsorption in MOR 15-P- 12 Modelling, ab initio cluster 15-0-04 Modelling, alkylation of aromatics 16-P-08 Modelling, cation sites 15-P-23 Modelling, chloroform adsorption 16-P- 14 Modelling, desulfurisation 15-P-22 Modelling, DFT 15-P- 10 Modelling, dynamical processes 15-O-02 Modelling, embedded cluster 15-0-04 Modelling, galiophosphate activation 16-P- 15 Modelling, hypothetical framework 16-P-07 Modelling methylation reaction 15-O-03 Modelling, MOR catalysis 15-P-12 Modelling proton mobility 15-0-01 16-0-04 Modelling reactivity 15-P- 15 Modelling, reaction mechanism 15-0-05 15-P-20 Modelling structure changes 15-P- 17 Modelling, synthesis, TS- 1 16-P- 16 Modelling, synthesis, zeolites 02-P-22 15-P-06 Modelling, transition state, cluster 15-P- 16 Modelling, zeolite framework 15-P-14 15-P-25 16-P-13 Modification, MCM-41 surface 17-P- 13 Modified H-MFI, alkylation catalyst 25-0-05 Molecular confinement 14-P- 12 Molecular dynamics, adsorption 16-P- 14 Molecular dynamics simulations 15-P-28 16-O-03 16-P-06 16-P-17 16-P-18
Molecular dynamics, experimental 13-P-06 Molecular dynamics, external surface 16-0-02 Molecular modelling 16-0-01 Molecular modelling, multicomponent diffusion 16-O-05 Molecular orbital calculation, Ag-LTA 14-O-04 Molecular simulation, transition state 15-P- 19 Molecular traffic control 16-0-05 28-0-01 Molybdate, Cu, structure 09-P-07 Molybdenum sulfides, mesostructured 1 I-P-11 Monolayer, LTA crystal/glass 20-0-01 Monomer for polyesters, synthesis 25-P-07 Monooctylamine, synthesis 23-P-07 Monte Carlo docking 16-P- 16 Monte Carlo energy minimisation 07-P-21 16-P-I 1 Monte Carlo Simulation 16-O-01 16-O-03 16-P-12 Montmorillonite support 27-P- 10 Montmorillonite tuff 3 l-P-11 MORacidity 12-P-05 12-P-14 13-P-08 MOR, acid site 14-P- 10 MOR, acid site NMR 13-P-23 MOR adsorbent 18-P- 15 19-P-06 MOR, adsorption modelling 15-P- 12 MOR, AI distribution 13-P- 19 MOR, AI in activated 13-P- 18 MOR alkylation catalyst 16-P-08 24-P-06 25-P-07 25-P-09 MOR, alkylation catalyst, modelling 15-0-03 MOR/alumina membranes 20-P- 18 MOR, applications 3 I-P-08 3 l-P- 15 MOR, Armenia 0 l-P- 16 MOR catalyst 28-P- 15 MOR, cation location 09-P- 13 MOR, Ce 29-P- 11 MOR, Co 27-P- 13 MOR, composition 03-P- 19 MOR, Cu 11 -P-20 27-P- 13 MOR, dealuminated 12-P- 16 MOR, dealuminated 11-P-25 12-P-05 29-P-11 MOR, dehydration 09-P- 13 MOR dehydration catalyst 23-P-08 MOR, diffusivity 19-P-08 MOR, Fe 04-P-I 5 13-P-32 27-P-13 30-P-11 30-P-27 MOR, H form 27-0-04 MOR, high-silica 02-P-39 MOR, host 22-P-08 MOR, In deNOx catalyst 10-O-01 MOR isomerisation catalyst 26-0-01 28-P- 13 MOR from magadiite 02-P-36 MOR membranes 20-0-03 MOR, morphology 03-P- 19 MOR, Ni 27-P- 13 MOR, Ni deNOx catalyst 30-P-30 MOR, occurrences 01-O-02 MOR, oxidation catalyst 27-P-08 27-P- 13 MOR, Pd, Heck catalyst 23-0-02
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MOR, Pd,Co,Ce 30-P-22 MOR photocatalyst 30-P-20 MOR porosity 26-P-20 MOR, Pt 26-P- 19 MOR ring opening catalyst 26-0-03 MOR, sigma transformation 16-P-07 MOR, synthesis 03-P- 19 MOR, structure modelling 16-P- 11 MOR, thermal stability 12-P-05 MOR, vibrational spectroscopy 16-P- 11 MOR, in zeolitic tuff 0 l-P-13 MOR, Zn 04-P-15 13-P-32 Morphology, effect on diffusion 19-O-04 Morphology, mesoporous silica PL- 1 06-P- 13 Morphology, MFI 02-P- 15 Morphology, MFI, internal 14-P-38 M0ssbauer spectroscopy 14-P-22 MPV (Meerwein-Ponndorf-Verley) reduction 23-P-33 08-P-06 MSU-S, synthesis from zeolite seeds 08-P-05 MSU-X 08-0-01 MSU-X in chromatography and filtration MTBE 28-P- 11 29-P-12 24-P-18 MTO, mechanism 24-P-28 MTO process 05-P-17 MTO on SAPO-47 05-P-18 MTO on SAPO-56 24-P-13 MTS polymer degradation catalysts 28-P-10 MTS, adsorbents 06-P-27 MTS, swelled 25-0-03 MTW alkylation catalyst 29-P-25 MTW, Fe oxidation catalyst 04-0-03 MTW, Fe, synthesis 03-P-10 MTW, Ga 26-P-16 MTW, Pt hydroconversion catalyst 02-P-27 MTW-related frameworks 11-O-03 Mu-2 by Mu-3 transformation 11-O-03 Mu-3 stability 16-O-05 Multicomponent diffusion, modelling 15-P-27 Multipole moment, substituted AIPO4 Multiquanta 2D 27A1MAS-NMR 13-P-18 Multiquanta MAS-NMR 13-0-03 13-P-24 27-O-01 MWW 13-0-04 MWW acidity 27-0-03 MWW, acid oxidation catalyst 28-P-15 MWW alkylation catalyst 10-0-02 MWW, basicity 23-P-27 MWW, Beckmann catalsyt 14-P-21 MWW, Co MWW, deNOx catalyst 30-P- 13 30-P-30 30-P-30 MWW, Ni 14-P-21 MWW, Fe 05-P-14 MWW, magadiite-intercalated MWW synthesis 02-P-34 02-P-42 03-P-13 27-O-01 MWW, Ti 14-P-21 MWW, trivalent distribution 32-0-04 Mycotoxin, adsorption
N 14N NMR, MFI synthesis 02-P-40 15N.NMR 13-P-22 N2 adsorption 17-P-05 N2 adsorption, AEL 17-O-03 12-P-09 N2 adsorption, IR 12-0-04 N2 adsorption, LSX 17-P-16 N2, supercritical adsorption, zeolites 17-P-15 N2/Ar adsorption, FAU 17-P-15 N2/Ar adsorption, LTA 18-P-13 N2/O2 selectivity of adsorption 30-0-02 N20 decomposition, Fe-MFI 30-P-13 NzO decomposition, MCM-22 27-0-03 N20 in oxidation 30-P-06 30-P-11 N20 reduction 30-P-14 N20 SCR with propene 16-P-20 N20-NO interaction 23Na 2D NMR 13-P-19 23Na MAS NMR 09-0-05 14-P-17 14-P-37 23Na MQ MAS NMR, Li,Na-FAU 13-P-12 23Na NMR, FAU adsorbent 12-P-12 23Na NMR, paramagnetic effect of 02 13-P-12 03-0-05 Na cations in synthesis 1 l-P-18 Na exchange 14-P-09 Na forms of zeolites, NO adsorption 12-P-12 Na,Li-FAU, pyrrole adsorption 12-0-04 Na-LSX 14-P-37 Na nanoparticles 14-P-37 Na-Rb alloy 13-P-16 Na-X, toluene adsorption NMR 16-O-03 Na-Y, adsorbent 22-P- 18 Nanoclusters, Pblz/LTL 2 l-K-01 Nanocomposite in zeolites Nanocrystailine FAU 02-0-03 02-P-14 Nanocrystalline MFI 02-0-04 28-P-08 22-P-13 Nanocrystals, anatase 02-P-12 Nanocrystals, offretite 06-P-27 Nanoemulsion template 03-P-14 Nanoparticles agglomerates, MFI 11-O-01 Nanoparticles, Au 07-P-13 Nanoparticles, Fe203 in MCM-41 21-P-10 Nanoparticles, SnO2 29-P-22 Nanoparticles, surfactant stabilized 29-P-17 Nanoparticles, ZrO2 in SBA-15 02-0-01 Nanoscopic precursor particles 02-0-04 Nanoslabs, silicalite- 1 22-0-05 Nanowires in FSM- 16 15-P-26 Nanowires, Se in MFI 26-P-23 Naphtha isomerisation 25-P-06 Naphthalene isopropylation Naphthalene alkylation 25-0-03 25-P- 13 25-P- 14 26-0-04 Naphthene ring opening 25-P-08 S-Naproxen synthesis
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Natrolite 09-P-09 Natrolite, applications 3 l-P-06 Natrolite, ion exchange 0 l-P-08 Natrolite, lattice vibrations 16-P- 19 Natural zeolites, Antarctica 0 l-K-01 Natural zeolites applications PL-2 0 l-P- 16 22-P-10 22-P-15 30-P-10 31-O-01 31-P-06 31-P-08 31-P-12 31-P-14 31-P-15 32-O-01 32-0-04 32-P-06 32-P-09 32-P-10 32-P-12 Natural zeolites, Armenia 0 l-P-16 Natural zeolites, Bulgaria 0 l-P- 13 Natural zeolites, Croatia 3 l-P- 11 Natural zeolites formation 01-O-02 01-P-06 01-P-10 01-P-13 Natural zeolites, Croatia01 -P- 17 Natural zeolites, Iran 01-P-08 3 l-P-06 Natural zeolites and health 32-O-01 32-P-09 Natural zeolites, Jordan 31-O-01 Natural zeolites, occurrencies 0 l-K-01 Natural zeolites, properties 01-O-05 Natural zeolites, Romania 0 l-P-09 Natural zeolites, Russia 0 l-P- 12 Natural zeolites, Sardinia 01-O-02 Natural zeolites, South Africa 3 I-P-12 Natural zeolites, Ukraina 3 l-P-08 3 I-P- 10 Natural zeolites, Zambia 3 I-P-12 Nb, see also Niobate Nb-MCM-41 07-0-04 24-P-12 27-P-09 Nb-MFI 01 -P- 14 Nb-MFI, synthesis 04-P- 10 Nb nanoparticles 14-P-37 Neopentane diffusion 19-0-04 Neutron diffraction 09-0-04 09-0-05 Neutron diffraction, adsorbed phase 17-O-02 Neutron diffraction, AEL adsorbent 17-O-03 NH3, adsorption on zeolites 18-P- 10 NH3 TPD, see TPD Ni-aluminophosphate 09-P-08 Ni-bentonite 18-P- 14 Ni clusters in MFI 04-P-06 Ni-ERI, oxidation catalyst 27-P- 13 Ni-FAU 24-P-17 24-P-24 Ni-FAU, oxidation catalyst 27-P-13 Ni-MCM-22, deNOx catalyst 30-P-30 Ni-MCM-41 hydrodechlorination catalyst 23-P-16 Ni-mesoporous silica 08-0-02 Ni-MFI 04-P-06 23-P-20 Ni-MFI, deNOx catalyst 30-P-30 NiMo/H-BEA 26-P-15 NiMo/H-Y 26-P-15 NiMo hydrotreatment catalysts 26-P-08 NiMo hydrotreatment catalyst on MCM-41 NiMo/MCM-41 hydrotreatment catalyst 26-P-12 26-P-14 NiMo sulfide/large pore zeolites 26-P-15 NiMo/Zr-HMS hydrotreatment catalyst 26-P-22 Ni-MOR, deNOx catalyst 30-P-30
Ni-MOR, oxidation catalyst 27-P- 13 Ni phosphates 05-P-08 Ni phosphate, VSB- I 22-0-03 Ni Raney/MFI composite 30-P-29 Ni,W/Y hydrocracking catalysts 1 l-P-08 Ni,Zn/MFI aromatisation catalyst 24-P-31 28-0-02 Ni/Zr-MCM-41 23-P-28 Ni/ZrO2 fuel cell catalyst 07-P-20 Nine-member rings 09-P- 12 Niobate molecular sieves 05-O-01 Niobium ammonium complex in MFI synthesis 04-P-10 NIR spectroscopy 27-P-11 Nitrate cancrinite 02-P-07 Nitrate removal 3 l-P- 15 Nitration 29-P-28 Nitration, aromatics 13-P-22 Nitration, zeolites 04-0-02 Nitrene 24-0-04 Nitriles, source of template 03-0-03 p-Nitroaniline, adsorption 13-P-06 Nitrogen industry, wastewater 30-P-34 3 I-P- 10 Nitromethane reagent 23-P- 13 Nitromethane, ~3C NMR probe 23-P- 13 N-Nitrosamines degradation 30-P-07 30-P-08 N-Nitrosamine removal 18-P-07 Nitroxide, ditert-butyl 14-P-07 Nittoxide EPR label 32-0-02 Nitroxide EPR probe 14-P-07 Nitroxide radical adsorption 14-P-07 Nitroxyl radical probe 13-P-09 NMR (see individual nuclei) NMR cristallography, AIPOa-CJ2 09-0-02 NMR, in-situ 02-P- 18 NMR spectroscopy 27-P-11 NMR, MCM-48 07-P-06 NO adsorption 12-P-15 14-O-05 14-P-09 NO adsorption,Co-MFI 10-P-08 NO decomposition 07-0-04 12-P-15 14-O-03 30-P-33 NO decomposition, photocatalytic 28-P-07 30-P-24 NO-NzO interaction 16-P-20 NO reduction 30-P-15 30-P-27 30-P-28 30-P-34 NO reduction with propene 30-P-14 30-P-30 NO2 adsorption 14-0-05 NO2 decomposition 07-0-04 12-P-15 14-O-03 30-P-16 30-P-33 NOx decomposition, photocatalytic 28-P-07 30-P-24 NOx abatement, AIPO4 catalysts 30-P-31 NOx adsorption 10-0-04 10-P-08 12-P- 15 14-0-05 14-P-09 NOx decomposition 30-K-01 NOx reduction 30-P- 10 30-P-15 30-P-25 30-P-27 30-P-28 30-P-34 NOx reduction by CH4 10-O-01 30-P-22 30-P-35 NOx reduction by NH3 30-P-12 NOx reduction in propane 10-O-04
423
NOx reduction by propene 30-P-14 30-P-30 NOx reduction with hydrocarbons 30-0-03 12-O-02 NOx sorption, metal zeolites 30-0-04 NOx storage, metal zeolites 30-0-04 Noble metal zeolite 23-P-20 Noble metals/MCM-41 26-P-07 Nonasil, synthesis 02-P-41 Non-ionic surfactant 06-P-23 08-0-02 Nu-86 synthesis 02-P-20 NU-88, cracking catalyst 26-P-11 NU-88, hydroconversion catalyst 26-P-11 NU-88, pore topology 26-P-11 nuclear waste 05-0-01 Nucleation agent, zeolitic 2 l-P-09 Nucleation and growth 02-P- 16 Nucleation, FAU 02-0-03 Nucleation, LTA 02-P-32 Nucleation, zeolites 02-0-02 Nucleophilic Substitution 23-P-07
O 170 3Q MAS NMR 14-0-02 170 DOR NMR 09-0-02 14-0-02 14-0-02 ~70 NMR chemical shitt 17-0-01 02 adsorption 17-O-03 02 adsorption, AEL 27-P-16 02 as anti-coke agent 27-P-16 02 and Beckmann catalyst deactivation 27-P-16 02 and catalyst lifetime 18-P-13 O2/N2 selectivity of adsorption 02, paramagnetic effect on 23Na NMR 13-P-12 27-P- 11 02, singlet, molecular 21-P-16 O2 substitution by organics 17-P-16 02, supercritical adsorption, zeolites 11-P-27 03 in calcination 29-P-18 03, template removal, MCM-41 10-O-03 Occluded salts 22-P-17 Occluded salts, LTA 05-0-01 Octahedral molecular sieves Octahedral-tetrahedral frameworks 05-P-16 05-P-20 09-P-07 1 l-P- 15 27-P-15 Octane enhancers 28-P-11 Octane, iso-, synthesis 24-P-20 Octanol, amination 23-P-07 Offretite, colloidal 02-P- 12 Offretite isomerisation catalyst 28-P- 13 Offretite single crystals 03-P-08 OH groups, ferrierite 13-P- 17 Olefin adsorption 12-P-06 Olefin epoxidation 11-P-29 14-P- 12 15-P- 18 24-P- 14 27-0-02 Olefin hydrogenation 29-P-22 Olefin isomerisation 26-P-09 Olefin oxidation, ETS- 10 11-O-04
24-P-15 Olefin polymerisation Olefination of haloaromatics 23-0-02 01-0-02 Oligocene Oligomerisation, acetylene 24-P-15 Oligomerisation, ethylene 24-P-17 24-P-15 Oligomerisation, olefins Optical properties 21 -O-03 05-P-12 Optical properties, Ce-Eu silicates 22-P- 18 Optical properties, PbI//LTL 22-P-14 Optical sensors 22-P-17 Optical spectra 22-P-07 optical switching 22-0-01 Optics, non-linear 23-P-22 Orange blossom fragrance 17-O-03 Ordering, adsorbed phases, AEL 01-P-07 Ordering, Al, in dachiardite 13-O-01 Ordering, B and AI 22-0-01 Ordering, non-centrosymmetric 04-P-12 Organic acid templates 17-P-06 Organic adsorption, FER 21-P-16 Organic framework Organic functionalisation, mesoporous silica 29-P-31 14-P-30 Organic probe molecules 20-P-12 Organic removal, membrane Organic-modified clinoptilolite 22-P- 12 22-P-15 Organometallic complexes, encapsulated 07-P-10 14-P-16 Organophosphates, microporous 22-0-02 Organozeolites 2 l-P- 16 Oriented crystal growth 02-P-28 Oriented crystals, mordenite 20-0-03 OSB-1 (OSO) 05-0-05 OSB-2 05-0-05 Over-exchanged Cu-ZSM 5 30-P-21 Oxalate in Fe-zeolite synthesis 04-0-03 Oxidation, alkanes, selective 27-O-01 Oxidation, aromatics 2 I-P-07 Oxidation, benzene to phenol 27-0-03 Oxidation, biological 3 I-P- 15 Oxidation catalyst, Fe zeolites 07-P- 10 Oxidation catalyst, substituted MCM-41 29-P-18 Oxidation, CO 29-P- 14 30-P- 10 Oxidation, CVOC 30-P- 18 Oxidation, cyclohexane 02-P-14 07-P-10 27-P-15 Oxidation, cyclohexene 2 l-P- 13 Oxidation, isobutanol 27-P- 13 Oxidation, Fenton 31-O-03 Oxidation, hydrocarbons 27-P-06 Oxidation, methane, photocatalytic 24-P- 12 Oxidation by N20 27-0-03 Oxidation, olefins 11-O-04 Oxidation, phenol 04-0-01 Oxidation, phytotoxic chemicals 31-O-03 Oxidation, propane, photocatalytic 28-P-07 Oxidation, propane, selective 27-P- 12 Oxidation, propyl alcohols 27-P-08
424
Oxidation, selective 24-P- 14 27-0-02 Oxidation, styrene 29-P-21 Oxidation, thioethers 27-P-09 30-P-26 Oxidation, toluene 30-P-23 Oxidation, total 30-P-09 Oxidation, VOC 30-P- 18 Oxides, mixed 24-P-26 Oxidizing atmosphere, effect on activation 14-P-38 Oxyhalogenation, aromatics 23-P-24
31p NMR 09-0-02 09-P- 11 11-O-03 13-P-20 13-P-24 14-P-11 18-P-13 02-P-40 31p NMR, MFI synthesis 11-P-23 P-treated zeolites 08-P-12 Packing parameter 01-P-10 aleogene 13-P-22 para selectivity, toluene nitration 26-0-02 Paraffin isomerisation 06-P-25 Parallel synthesis 13-P-12 Paramagnetic effect of 02 on 23Na NMR 14-P-07 Paramagnetic radicals 28-P-08 Para-selectivity 29-P-12 Partially crystalline BEA 19-O-05 Particle effects, membranes 02-P-23 Particle size, BEA 10-P-09 Passivation, MFI 212pb radiotracer 3 l-P-06 22-P-18 PbI2 nanoclusters in LTL 11-O-01 Pd-Au/H-Y 23-P-26 Pd/BEA 30-P-22 Pd and Ce promoter 23-0-02 Pd/FAU, Heck catalyst 23-P-23 Pd/K,Na-X 27-P-08 Pd/LTA, oxidation catalyst 23-0-02 Pd/LTL, Heck catalyst 29-P-22 Pd/MCM-41 24-O-01 Pd/MeAPSO- 1 l 23-P-26 Pd/MOR 23-0-02 Pd/MOR, Heck catalyst 22-0-05 Pd nanowires 29-P-13 Pd, Pt on mesoporous carbon 24-O-01 Pd/SAPO- 11 27-0-05 Pd-Pt/Y hydrogenation catalysts 23-P-26 Pd/Y 26-P-20 n-Pentane conversion 19-0-04 Pentane, neo-, diffusion 30-P-09 Pentane, total oxidation 19-O-05 Permeability, composite membrane 20-P-07 Permeance, membranes 27-P-10 Peroxide decomposition, biomimetic PL-4 Petrochemistry evolution 1 l-P-10 pH, effect on alumination 31-P-11 pH effect on ion exchange
pH effect, MCM-41 synthesis pH indicators pH of synthesis Pharmacosiderite Phase change, zeolites Phase diagram Phase transformation, aluminium methylphosphonate
06-P-28 22-P-21 02-P-19 1 l-P-15 10-P-07 03-P- 18
21-P-17 Phase transformation, Mu-3 11-O-03 Phase transition, confined system 17-O-01 17-P-17 14-P-16 Phase transition, host-guest systems 2 l-P-09 Phase-change material Phenol alkylation 23-P-31 25-0-02 25-P-09 28-P-15 29-P-08 Phenol dehydroxylation Phenol hydroxylation 07-P-07 27-P-17 04-0-01 Phenol oxidation 20-P-12 Phenol removal, membrane 27-0-03 Phenol, synthesis Phenol-trimethylbenzene transalkylation 25-0-04 07-0-02 Phenyl-functionalized mesoporous silica 1-Phenyl- 1,2-propanedione hydrogenation 23-P-25 32-0-05 Pheromones 01 -O-05 PHI, cation exchange 01-O-04 PHI, Li 04-0-03 Phosphate in Fe-zeolite synthesis 02-P-40 Phosphate in MFI synthesis 22-0-03 Phosphate, Ni, VSB- 1 16-P-15 Phosphates, Ga, stability 32-0-03 Phospholipids 09-P-14 Phosphonate, AI methyl, polytypism 14-P-20 Phosphorescence spectra 31-P-14 Phosphorus removal 05-P-15 Phosphites, aluminium, microporous 30-P-16 Photocatalysis, NO2 decomposition Photocatalysis, transition metal oxides in zeolites 30-K-01 Photocatalytic decomposition, NO 28-P-07 30-P-24 Photocatalytic degradation 30-P-20 Photocatalytic oxidation of methane 24-P- 12 Photocatalytic oxidation of propane 28-P-07 Photocatalytic synthesis of H202 27-P- 14 Photochemical H20 decomposition 28-0-03 photochromic dye 22-P-07 Photoluminescence 14-P-20 14-P-35 21-O-03 21-O-05 29-P-30 Photolysis of alkyl ketones 15-P-07 Photonic devices 22-P-20 Photophysics 22-P-09 Photo redox system 24-P-07 Phtalocyanine 22-P-06 Phtalocyanine in FAU 14-P-12 Phytotoxics oxidation 31-O-03 Pigments, encapsulated 22-P- 19 Pillared clay 22-P- 16 Pillared clays, alkylation catalyst 25-P-13
425
Pillared magadiite Pillared bentonite Pillaring Alpha-Pinene derivatives Alpha-Pinene epoxidation Alpha-Pinene hydration Pinene oxide, rearrangement Piperidine, formation Plant growth enhancenent Plasma activation Plasma treatment, FAU Polarity effects Polluted river water Polyamine binders Polyaromatics adsorption Polyaromatics alkylation Polyaromatics ionisation Polyethylene binder Polyethylene conversion Polyethylene cracking Polyethylene degradation Polymer degradation Polymerisation, acetylene Polymerisation catalysts Polymerisation, ethylene Polymerisation, olefins Polymer-zeolite membrane 21-P-12 Polystyrene beads support Polytypism, BEA 02-P-24 Population balance Pore mouth catalysis Pore mouth plugging, MFI Pore mouthing, BEA Pore mouthing, MFI Pore size distribution, modified MCM-41 Pore size, effect on adsorption Pore size, effect on isomerisation Pore size expansion, see swelling Pore size, MCM-41 Pore structure, ERS- 10 Pore topology, NU-88 Porosils, host Porosils, synthesis Porosity, hierarchical Porous glass, Beckmann catalyst Positron annihilation Positron emission profiling Post-synthetic treatment 06-P-06 08-P-13 Powder diffraction 01-O-04 Pressure effect on natrolite Pressure effect on zeolite structure Pressure swing adsorption (see PSA) Probe, ~3C NMR, nitromethane Propane adsorption Propane formation Propane selective oxidation Propane, photocatalytic oxidation
23-P-18 22-P-16 09-P-08 23-P-14 23-P-14 23-P-19 23-P-14 23-P-08 31-O-02 1 l-P-14 1 l-P-17
18-P-07 31-P-15 20-0-01 14-P-18 25-O-01 14-P-18 22-P-15 24-P-13 30-P-17 24-P-25 30-P-17 24-P-15 24-P-08 24-0-05 24-P-15 19-O-05 21-P-15 0 l-K-01 02-P-29 26-0-02 11-O-02 1 l-P-09 11-P-24 17-P-13 17-P-07 25-P-08 12-P-11 29-0-01 26-P-11 10-O-03
02-P-41 21-P-07 27-P-16 12-P-11 19-P-10 1 l-P-16 09-P-09 16-P-19 09-P-09 23-P-13 18-0-04
24-0-02 27-P-12 28-P-07
Propane/propylene, separation 18-0-04 n-Propanol adsorption 18-P- 15 2-Propanol conversion 29-P-05 Propyl alcohols oxidation 27-P-08 Propylene adsorption 18-0-04 Propylene in alkylation 25-P- 14 Propylene in deNOx SCR 30-P-30 Propylene dimerisation 24-P-24 Propylene epoxidation 24-P- 14 27-0-02 Propylene oxide 24-P- 14 Propylene polymerisation 24-P-08 Propylene/propane, separation 18-0-04 Protein adsorption 23-P- 17 Proton mobility modelling 15-0-01 Proton positions, FAU 09-0-04 Proton transfer, modelling 15-0-02 Proton tunnelling, FAU 16-0-04 PSA, CO2 18-0-01 PSA separation, ethyl acetate 18-P-12 Pt,Au/H-Y 11-O-01 Pt-2,2'-bipyridyl complex 24-P-29 Pt catalysts 29-P- 19 Pt dispersion 26-P- 16 Pt/BEA 17-P-08 24-P- 16 Pt/BEA aromatisation catalyst 15-P-09 Pt/BEA hydrogenation catalyst 26-P- 13 Pt/BEA isomerisation catalyst 20-P- 18 Pt/Cs-BEA reforming catalyst 26-0-05 Pt/CsX basic catalyst 23-0-05 Pt-FAU 17-P-08 Pt-FAU aromatisation catalyst 15-P-09 Pt/FAU bifunctional catalyst 30-0-05 Pt/FAU catalyst, CH2C!2 conversion 30-0-05 Pt/K-LTL catalyst 1 l-P-07 Pt-LTL aromatisation catalyst 15-P-09 Pt/MAPSO-31 hydroisomerisation catalyst 26-P-06 Pt/MCM-41 chiral hydrogenation catalyst 23-P-25 26-P-21 Pt/MCM-41 hydroisomerisation catalyst Pt/MOR, diffusivity 19-P-08 28-0-05 26-P-19 Pt/MOR isomerisation catalyst 27-0-04 Pt/MOR hydrogenation catalyst 28-0-05 Pt-MOR hydroisomerisation catalyst Pt/MFI 17-P-08 23-P-20 26-P-16 Pt/MTW hydroconversion catalyst 14-P-36 Pt,Ni/USY isomerisation catalyst 29-P-13 Pt, Pd/mesoporous carbon 27-0-05 Pt-Pd/Y hydrogenation catalysts 22-0-05 Pt-Rh catalysts 26-0-03 (Pt,Rh,Pd,Ru,Ni)/HZSM-5 26-0-04 Pt zeolites, hydrogenation catalyst 29-P-15 Pt-Zn/zeolite X 03-P-08 Pyrocatechol in zeolite synthesis 2 l-P-08 Pyrolysis 12-P-12 Pyrrole adsorption, Li,Na-FAU
426
Q Quadrupolar interaction, ~B Quantum chemical calculations Quantum confinement Quantum confinement, Ag-LTA Quantum-chemical calculations Quinoline, fluorescence Quinone/BEA photocatalysts
13-P-11 14-0-03 21 -O-03 21 -O-05 14-0-04 15-O-05 13-P-13 27-P-14
R Radical sites 24-P-25 Radicals, adsorbed 24-P-07 Radicals, health effect 32-0-02 Radioanalytical methods 3 l-P-06 Radionuclides 3 l-P-05 32-P-12 Raman spectroscopy 14-P- 18 14-P-24 Raman spectroscopy, host-guest interactions 14-P-16 Raman spectroscopy, NIR 14-P-31 Raman spectroscopy, vanadium 14-P-33 Raman spectroscopy, zeolite lattice 12-P- 10 Raney metal/MFI composite 30-P-29 Rare earth exchange 1 l-P-19 Rare earth silicates 05-P- 12 Raspberry ketone 25-0-02 STRb NMR 14-P-37 Reaction dynamics, proton transfer 16-O-04 Reactivity enhancement 28-0-01 Reactivity index 15-P-06 Reactivity, silicalite 15-0-05 Rearrangement of pinene oxide 23-P- 14 Reconstructive transformation 02-P-25 REDOR MAS NMR 13-0-01 13-P-23 Redox behaviour, Fe in MCM-41 07-0-03 Redox behaviour, Ga-FAU 10-P-06 Redox ion exchange 09-P- 10 Redox mesoporous molecular sieves 23-P- 14 Reductibility, Cu/ZSM-5 27-P- 12 Reduction, Cu 2+in MFI 30-P-21 Reduction, Ga in FAU 10-P-06 Reduction, metal ions 04-0-01 Reduction, regioselective, ketones 23-P-33 Refining evolution PL-4 Reflection, internal 21-O-04 Reforming, FCC gasoline and LCO 26-0-05 Relaxation, lattice 16-P- 18 Relaxation processes, cations 14-P-06 Renewable feedstock 23-P-32 REPDOR triple resonance 13-O-01 Resin-silicate composite 03-P-07 Resonance Raman spectroscopy 14-P-34 RHO, dealumination 11-P-25 Rietveld analysis, molecules in zeolites 16-P-06
Rietveld refinement 09-0-01 01-O-04 05-P- 19 09-P- 11 Rietveld refinement, mesoporous silicas Ring opening, aromatics Ring opening, cyclohexane Ring opening, epoxides Ring opening, methyloxirane Ring opening, naphthenes 3-Rings Rings, penetrability Roboting synthesis Romania, clinoptilolite occurrences Ru bipyridyl complexes/FAU RUB-29 lithium silicate Rubidium clusters in LTA Russia, clinoptilolite tuff
Salen complex anchoring Salen complexes, Co, on MCM-41 Salen complex, Yi (IV), chiral Salt occlusion, PbI2/LTL SANS, synthesis SAPO-5 SAPO-5, amination catalyst SAPO-56 SAPO-I 1 alkylation catalyst SAPO-I 1 dehydroisomerisation catalyst SAPO-11 synthesis SAPO-I 1 amination catalyst SAPO-31 alkylation catalyst SAPO-31 amination catalyst SAPO-31, synthesis SAPO-34 MTO catalyst SAPO-34, acidity SAPO-34, amination catalyst SAPO-34, Fe SAPO-34, host SAPO-37, acid site SAPO-37, thermal decomposition SAPO-41 alkylation catalyst SAPO-47, characterisation SAPO-47, synthesis Saponite, reagent Sardinia, zeolite occurrences Saturation, unsaturated rings SAXS, synthesis SBA-1, functionalized, synthesis SBA-1, Mo SBA- 1, synthesis SBA-2, functionalised SBA-3 in HPLC SBA-3 synthesis
09-P-14 08-P-14 26-P-13 26-0-03 23-P-10 23-P-15 26-0-04 O5-0-O5 15-P-14 03-K-01 0 l-P-09 28-0-03 09-0-O5 21-P-18 01-P-12
29-P-08 23-P-10 23-P- 11 22-P-18 02-0-01 13-P-14 23-P-07 05-P-18 23-P-31 24-O-01 02-P-13 23-P-07 23-P-31 23-P-07 04-P-09 24-P-28 24-P-26 23-P-07 30-P-27 24-P-26 14-P-10 14-P-11 23-P-31 05-P-17 05-P-17 06-P- 15 01-O-02 26-P-10 02-0-01 07-0-02 14-P-26 06-P- 18 07-P-17 18-P-06
06-P-28
427
SBA-3, Mo 14-P-26 SBA-3, synthesis 06-P- 18 SBA-6, HRTEM PL-5 SBA-15 08-P-07 SBA- 15, adsorbent 17-0-01 SBA- 15, AI, cracking catalyst 08-P- 13 SBA-I 5, AI, Pt hydroisomerisation catalyst 08-P- 13 SBA- 15, AI, template interaction 08-0-04 SBA-15 host 29-P-17 SBA- 15 in HPLC 18-P-06 SBA- 15 porosity 08-0-03 SBA-15, stability 08-P-13 SBA- 15, V, photocatalyst 24-P-07 SBA- 15, wall properties 08-P- 14 SBA- 15, Y, HRTEM PL- 1 Scaffolding 7-P- 11 Scolecite 09-P-09 Sea water 3 l-P- 16 Sea water, bentonite zeolitisation 03-P-06 Secondary synthesis, mesoporous silica 08-P-11 Sedimentary zeolites, properties 01-O-05 Sedimentary zeolites, volcano01-O-02 Seeding 02-P-08 02-P-19 02-P-20 02-P-31 Seeding, effect on synthesis 02-P-21 Seeding, film 20-P-09 20-P-16 Seeding, zeolite layers 20-0-02 Selectivation by coke 28-P-06 Selectivity, diffusion-controlled 28-0-01 Selenium, nanowires in MFI 15-P-26 SEM ETS- 10 27-P- 15 Semiconductor, MoS I l-P-11 Semiconductors, magnetic 21-O-03 Semi-empirical quantum-mechanical method 16-P-16 Semiochemicals 32-O-05 Sensor, calorimetric 22-P-11 Sensor, gas 2 l-P- 10 Sensor, optical 22-P- 14 Separation, cafeine 20-0-05 Separation, CO2 18-0-01 Separation, CO2/C2 hydrocarbons 18-O-03 Separation of mixtures 17-P- 16 Separation, membrane 19-0-05 Separation, membrane, asymmetric 23-P- 10 Separation, propane/propylene 18-0-04 Separation, xylenes 18-P-08 SF6-Xe diffusion in BOG, modelling 16-O-05 Shape selectivity 11-P-24 25-P-07 25-P-09 25-P- 14 28-P-08 28-P- 13 29-0-01 29-P- 11 Shape selectivity enhancement 10-P-09 Shape selectivity simulation 15-P-19 16-O-01 16-P-08 Shape selectivity, test reactions 26-P-11 Shape-selective alkylation 25-0-01 Ship-in-the-bottle complexes 07-P-10 14-P-12 21-K-01 21-P-11 22-P-07 22-P-09 24-P-29 27-P-10
295i 2D NMR 13-P- 19 29Si NMR 0 l-P-07 03-0-04 04-P- 18 09-0-01 1 I-P-07 l l-P-21 18-P-13 13-P-06 13-P-10 30-P-19 29Si NMR, MFI synthesis 02-P-40 29Si NMR, spectra prediction 15-P-25 Si/A1 distribution, clinoptilolite PL-2 Si/AI ratio, dealuminated Y 13-P- 15 Si/AI ratio, effect of alkalinity 03-P- 19 SiC nanoparticles 21-O-05 Sigma transformation 16-P-07 Silane, functionalisation by 29-P- 16 Silane, hydrophobisation by 06-P-06 Silane, methylene framework 2 I-P- 16 Silica adsorbents 18-0-04 Silica aggregates, fractal 14-P-25 Silica deposits 28-P-08 Silica fibers, zeolitisation 02-P-26 Silica MTS 06-P-27 Silica source 02-P-I 9 02-P-20 06-P- 15 Silica source, effect on synthesis 02-P-23 Silica source, effect on synthesis of MOR 03-P- 19 Silica spheres with Cu 07-P-07 Silica template 07-P-22 Silica BEA, pure 02-P-35 Silica, CaCI2 impregnated 31-O-04 Silica, HLS 02-P-25 Silica, reagent 02-P- 13 Silica-alumina, amorphous 27-0-05 silica-alumina, amorphous catalyst 28-P- 15 Silica-alumina, Beckmann catalyst 27-P- 16 Silicalite- 1 (see also MFI) 0 I-P- 14 Silicalite-1 adsorbent 17-0-02 19-0-02 Silicalite-1, adsorption modelling 16-P-10 16-P-12 Silicalite- 1, diffusion 19-P- 10 Silicalite- 1 film 20-0-04 Silicalite-1 membrane 03-P-17 19-O-05 20-0-02 Silicalite- 1 nanoslabs 02-0-04 Silicalite, supercritical adsorption 17-P- 16 Silica-rich mordenite 02-P-39 Silica-zirconia, mesoporous 07-P-09 Siliceous ferrierite 17-P-06 Silicon incorporation in SAPO 23-P-31 Silicon nanoparticles 21-O-05 Silylation, effect on diffusivity 19-0-03 Silylation, MCM-41 29-0-02 Silylation, mesoporous silica 18-P-06 29-P-31 Silylation, MFI 11-O-02 Silylation, Ti-BEA 11-P-29 Simulation, FAU (111) surface 16-0-02 Single crystal mesoporous 07-P-15 Single crystals, offretite 03-P-08 Single file diffusion 28-0-01 Single file diffusion in MOR 28-0-05 Single file diffusion, effect on catalysis 28-0-05 Singlet molecular oxygen 27-P-11 Sintering in membrane preparation 03-P-17
428
Smectite adsorbent 32-0-04 Smectite, reagent 06-P- 15 Sn NMR 05-P-13 21-P-10 SnO2 in Zeolites 05-P-13 Sn silicates 19-P-06 SO2 adsorption, effect of water 18-P-10 SO2 adsorption on zeolites 30-P-25 SO2, effect on DeNOx activity 29-P-25 SO2 oxidation 08-P-10 SO3H- anchored on mesoporous silica 09-P- 11 SOD AIPO4-20 02-P-28 SOD-CAN composite 02-P-28 SOD-CHA composite 15-P-08 SOD, encaspsulation, modelling 18-P-10 SOD from fly ash SOD, 170 NMR 14-0-02 22-P- 19 SOD, sulfide host 02-P-29 SOD synthesis 02-P-25 SOD synthesis, solid state 02-P-25 SOD, TMA 07-P-21 Sodalite building blocks 16-P-17 Sodalite cage 31-O-01 Soil amendment 14-P-25 Sol-gel, silica 29-P-12 Solid acid catalysts, partially crystalline 10-P-06 Solid state cation exchange 17-P-17 Solidification, confined phase 10-P-08 Solid-state cation exchange Solid-state reactions by microwave heating 1 I-P-13 18-P-07 Solvent effects 07-P-12 Solvent extraction, mesoporous Ti02 SOMS (Sandia octahedral molecular sieves) 05-O-01 06-P-14 Sonochemistry in synthesis 29-0-01 Spaciousness index 03-P-07 Sphares, silicalite 06-P-13 Spheres, mesoporous silica 2 l-P-06 Spheres, MFI, hollow 21-P-12 Spheres, zeolite, hollow 14-P-10 Spin echo double resonance 10-P-07 Spinel ceramic from zeolites 22-P-07 Spiropyrane in zeolite Y Sr exchange 05-0-01 1 l-P-18 Sr2+ removal 05-O-01 02-P-21 Sr, K-KFI, synthesis 1 l-P-16 SSZ-33 (-CON) 02-P-30 SSZ-35, synthesis 26-0-05 SSZ-42 03-0-03 SSZ-53 03-0-03 SSZ-55 05-0-03 STA-6 (SAS) 05-0-03 STA-7 (SAV) 05-0-03 STA-8 31-P-13 Stabilisation in cement matrix 13-P-20 Stability of AIPO4 vs. hydration 01-O-03 Stability, clinoptilolite 29-0-02 Stability, functionalized MCM-41 06-P-06 Stability, MCM-48
Stability, mesoporous alumina 06-P-23 Stability, mesoporous silica 06-O-01 06-P-06 06-P-07 08-P-06 08-P-14 Stability, SBA-15 08-P-13 Stability, substituted MCM-41 06-P- 19 Stability, thermal, FAU 1 I-P-13 Stability, thermal, SAPO-37 14-P-11 Statistical mechanics treatment, adsorption 16-P-10 Steam dealumination 1 I-P-08 13-P-07 28-P-08 Steam reforming 24-P-23 Steamcracker feed, synthetic 26-P-10 STF (see SSZ-35) Stirring, effect on synthesis 02-P-19 Storage, chromium 31-P-13 Storage, heat 2 l-P-09 31-O-04 17-P-10 Storage, Hz Storage, NOx 30-0-04 Strawberry crop enhancement 31-O-01 Structural modelling 08-P- 14 15-P-25 09-0-02 Structure analysis by NMR data Structure determination 01-O-04 05-0-02 05-0-05 05-P-06 05-P-10 05-P-11 05-P-16 05-P-20 09-0-04 09-P-08 09-P-09 1 l-P-12 09-0-03 Structure, FOS-5 Structure, packing parameter 08-P-12 Structure prediction 07-P-21 Structure, rare earth silicates 05-P-12 PL-5 Structure resolution, HRTEM 08-0-03 Structure, SBA- 15 16-P-07 Structure, sigma transformation 11-O-03 Structure transformation, Mu-3 Structure-directing agent (see template) 29-P-08 Styrene epoxidation 29-P-21 Styrene oxidation 1 l-P-11 Sulfides, mesoporous 22-P-19 Sulfide pigments 29-P-28 Sulfonation 08-P-lO Sulfonic acids, supported 27-P-09 Sulfoxidation, thioethers 26-P-06 Sulfur effect on catalysis 18-P-14 Sulfur guard PL-4 Sulfur in refining 27-0-05 Sulfur resistance 27-0-04 Sulfur tolerance 29-P-25 Sulfuric acid synthesis 2 l-P-09 Supercooling avoidance 17-P-16 Supercritical adsorption, zeolites 20-0-05 Supercritical CO2 extraction 07-P-09 Supercritical ethanol synthesis 17-P-05 Supercritical fluid, adsorption 30-P-12 Support effect in DeNOx SCR 29-P-13 Supported metals 29-P-16 Surface modification by silanes 1 l-P-17 Surface modification, FAU 29-P-09 Surface modification, mesoporous silica 14-P-08 Surface properties, Mo-zeolites 32-0-02 Surface reactivity
429
Surface species, ethylene conversion 24-P- 10 Surface structure, FAU (111 ) 16-0-02 Surface topography, SSZ-24 02-0-05 Surfactant extraction 06-P-11 Surfactant on clinoptilolite PL-2 Surfactant removal, mesoporous TiO2 07-P- 12 Surfactant, adsorbed adsorbent 06-P-27 32-0-04 Surfactant, cationic 06-P-09 Surfactant, deca(oxyethylene)oleyl ether 08-0-02 Surfactant, mixed 08-P- 12 Surfactant, non-ionic 08-0-03 08-P-05 08-P-11 08-P-12 06-P-18 Surfactants, triblock copolymers 08-P-07 Surfactant-silica interaction 08-P-05 SUZ-4, isomerisation catalyst 24-P-21 Swelled mesoporous silica 06-P-27 Swelling agents 06-P-27 17-P-05 Swelling agent, amine 06-0-04 Swelling, MCM-48 06-P-06 Sylilation, MFI 10-P-09 Synchrotron diffraction 01-O-03 09-P-09 09-P- 13 20-0-04 Synthesis, acidic, mesoporous silica 29-P-16 Synthesis, aging effect 02-P-19 02-P-21 02-P-29 Synthesis, AIPO4, additives 02-P-33 Synthesis, AIPO4, intermediates 02-P-11 Synthesis AIPO4-31, substituted 04-P-09 Synthesis, AI-SBA- 15 08-0-04 Synthesis, AI source, effect of 02-P- 19 Synthesis, alternate silica and surfactant 08-P-09 Synthesis, anatase nanocrystals 22-P- 13 Synthesis, asymmetric, terminal epoxides 23-P-10 Synthesis, BEA 02-P-23 Synthesis, BEA, all-silica 02-P-35 Synthesis, BEA, Cr, AI 04-P-08 Synthesis, cancrinite 03-P- 11 Synthesis, cation effect 03-0-05 Synthesis, clear solution 02-0-02 02-P-29 20-P-16 Synthesis, combinatorial methods 03-K-01 03-P-12 03-P-13 03-P-16 03-P-18 06-P-25 Synthesis, Co-MFI 04-P- 18 Synthesis, cosurfactants 06-P- 18 Synthesis, CrAPO-5 04-P- 12 Synthesis, dry-gel conversion 03-P- 10 Synthesis, ETS-4 04-P- 16 Synthesis, FAU 02-0-03 Synthesis, FAU film 20-P-16 Synthesis, Fe-MFI 04-0-03 Synthesis, Fe-MFI, fluoride 04-P-17 Synthesis, Fe-MOR 04-P- 15 Synthesis, Fe-MTW 04-0-03 Synthesis, FER 03-P-09 Synthesis, Fe-TON 04-0-03 Synthesis, fluoride medium 05-0-02 05-P-08 Synthesis, FOS-5 09-0-03 Synthesis by gel impregnation 04-P-07 Synthesis gel, thermal treatment 02-P-32
Synthesis, GUS- 1 02-P-27 Synthesis, IFR 03-0-04 Synthesis, K,Na-EDI 03-0-05 Synthesis, K,Na-FAU 03-0-05 Synthesis, K,Na-LTA 03-0-05 Synthesis, KFI 02-P-21 Synthesis, LTA 02-P-29 02-P-32 Synthesis, LTA film 20-P- 16 Synthesis, LTA, in-situ 18-P-09 Synthesis, LTL, alkaline earth effect 02-P-17 Synthesis, layer-by-layer 2 I-P- 12 Synthesis, layered germanates 09-P- 12 Synthesis, M41 s 07-P-24 Synthesis, MCM-22 02-P-34 03-P- 13 Synthesis, MCM-41 06-0-01 07-P-24 Synthesis, MCM-41, aging, effect of 06-P-21 Synthesis, MCM-41, aluminosilicate 06-P-08 Synthesis, MCM-41, Ce 07-P-23 Synthesis, MCM-41, Fe 06-P-28 Synthesis, MCM-41, substituted 06-P- 19 29-P-21 Synthesis, MCM-41, time of 06-P-21 Synthesis, MCM-41, Zr 29-P-24 Synthesis, MCM-48 06-O-01 06-P-06 06-P-24 Synthesis, MeAPO 05-0-03 Synthesis mechanism 02-P- 18 Synthesis, mesoporous alumina 07-P-08 07-P-I 8 Synthesis, mesoporous silica 06-P-07 06-P-09 06-P- 15 06-P-I 8 06-P-26 08-P-I 1 08-P-12 17-P-05 Synthesis, mesoporous silica, pH effect 06-P-20 Synthesis, mesoporous silica, functionalized 07-0-02 08-P-08 Synthesis, mesoporous silica, temperature effect 06-P-26 Synthesis, mesoporous zirconia 7-P-11 Synthesis with methylamine 04-O-01 Synthesis, MFI 02-O-01 02-P-09 02-P-15 Synthesis, MFI, bulk-material dissolution 02-P-26 Synthesis, MFI in carbon matrix 03-0-02 Synthesis, MFI on cordierite 30-P-33 Synthesis, MFI, Nb 04-P- 10 Synthesis, MFI, phosphate-affected 02-P-40 Synthesis, MFI, solid state 04-P-06 Synthesis, MFI, supported 20-P- 17 Synthesis, MFI, Zn 04-P- 14 Synthesis, microwave 0 l-P- 14 02-0-02 02-P-08 03-P- 15 Synthesis, MIL-34 05-P- 19 Synthesis, models 02-P-24 Synthesis, MOR 02-P-39 03-P-19 Synthesis, MOR from magadiite 02-P-36 Synthesis, MOR, Zn 04-P- 15 Synthesis, MSU-X, two-step 08-P-05 Synthesis, MWW 02-P-42 Synthesis, nanocrystalline FA U 02-P- 14 , Synthesis, non-aqueous media 05-P-08 05-P-11 Synthesis, organozeolite 2 I-P- 16
430
Synthesis, oxide mesostructures 07-0-05 Synthesis, parallel 03-P- 12 Synthesis parameters 02-0-02 02-P-08 02-P-20 Synthesis, particulate precursors 02-O-01 Synthesis, pH effect 06-P-28 Synthesis, phosphates, substituted 05-P-11 Synthesis, phosphates, Ti 05-0-02 Synthesis, phosphates, W 05-P-20 Synthesis, porosils 02-P-41 Synthesis, rare earth silicates 05-P- 12 Synthesis, SAPO- 11 02-P- 13 Synthesis, SBA-15 08-0-04 08-P-07 Synthesis, seeding, effect of 02-P-21 Synthesis, silica source, effect of 02-P-19 Synthesis, silicalite on resin 03-P-07 Synthesis, silicalite, clear solution 02-P-16 Synthesis, single crystals 03-P-08 Synthesis, SOD, solid state 02-P-25 Synthesis, sol-gel 0 I-P- 14 07-P-07 Synthesis, solvothermal 05-P-09 Synthesis, SSZ-35 02-P-30 Synthesis, stannosilicates 05-P- 13 Synthesis, static 02-P-34 Synthesis, stirring, effect of 02-P- 19 Synthesis, zeolites, supported 2 l-P- 12 Synthesis, temperature dependence 02-P-34 03-P-12 Synthesis, TON 02-P-22 02-P- 10 04-0-04 Synthesis, two-stage 02-0-03 02-P-34 Synthesis, ultrasound 06-P- 14 Synthesis, vanadosilicates 04-0-05 Synthesis, variable-temperature 20-P-07 Synthesis, zeolites from bentonite 03-P-06 Synthesis, zeolites from fly ash 18-P- 10 Synthesis, zeolites from MCM-41 07-P- 10 Synthesis, zeolites, modelling 02-P-22 15-P-06 Synthesis, zeolites, substituted 05-P-I 1 Synthesis, ZSM-34 02-P-22
Ta-MFI Tantalum-pillared magadiite Tartrate complexes Tb[(CIBOEP)4P](acac) encapsulation TBHP in epoxidation TEM TEM, 3 D TEM Pt,Ni-USY TEM, overgrowth TEM-EDX Temperature effect on ion exchange Temperature effect on MCM-41 synthesis Temperature effect, FAU surface Temperature effect on synthesis
01-P-14 23-P-18 29-P-08 22-P-09 29-P-30 23-0-05 14-0-01 14-P-36 02-P-06 26-P-15 1 l-P-18
06-P-26 16-0-02 02-P-21
Template (for mesoporous materials s e e also surfactant) 02-P-20 Template, alkali cations 03-P-18 Templates, AIPO4 synthesis 02-P-33 Template, amine 03-0-03 05-0-02 07-0-05 Template, butylamine 05-P- 17 Template, chiral 05-0-04 Template, colloidal 07-P-22 Template, concentration effect 02-P-41 Template cyclobutylamine 05-P- 19 Template, DABCO-based 02-P-27 Template degradation 02-P-22 11-P-27 20-P-38 Template degradation, MFI 14-P-38 Template, diethylenetriamine 02-P-41 Template, dodecylamine 29-P-08 Template, ethylenediamine 05-P-08 09-P-08 Template, ex nitriles 03-0-03 Template extraction 06-P-11 Template, hexamethylenediamine 02-P-22 02-P-42 16-P-16 Template, N-methyl hexahydrojulodinium 02-P-30 Template modelling 16-P- 16 Templates, multiple 04-P- 12 Template, nanoemulsion 06-P-27 Template, nitrate 02-P-07 Template, non-ionic surfactant 08-0-03 Template ordering 22-0-01 Template, organic acids 04-P- 12 Template, organic, choice 16-P-07 Template removal, gallophosphates 16-P- 15 Template removal, MCM-41 29-P- 18 Template removal, ZSM-5 13-P- 10 Template, silica 07-P-22 Template, tetrahydrofuran 03-P-09 template-trivalent interaction 13-O-01 TEOS, CVD on MFI 10-P-09 Terpene valorisation 23-P-29 Tert-butylation of biphenyl 25-P-07 Tetraalkylammonium degradation 20-P-38 2,4-di-Tetrabutylphenol, reagent 25-P- 12 Tetrachloethylene adsorption, MFI 17-O-02 Tetrafluoromethane reagent 1 l-P- 17 Tetrahydrofuran adsorption 12-P-08 Tetrahydrofuran template 03-P-09 Tetrapropylammonium cation 14-P-29 Texture SBA- 15 08-0-03 TG/DTA-MASS fluorinated FAU 1 l-P- 17 TGA 12-P-16 20-P-15 Therapy, adjuvants 32-P-09 Thermal activation, clinoptilolite 3 l-P-09 Thermal analysis, ETS-4 04-P- 16 Thermal behavior, clinoptilolite 11-P-26 Thermal desorption 17-P-09 Thermal stability, FAU 1 l-P-13 Thermal stability, MOR 12-P-05 Thermal stability, zeolites 10-P-07 Thermal treatment, MFI 14-P-38
431
Thermochemical storage of heat Thioether sulfoxidation Thiol-functionalized SBA-2 Thiophene cracking, modelling Thiophene HDS 26-P-17 Ti (IV) Salen complex, chiral Ti in AIPO4-31 Ti-BEA 27-P-11 Ti-BEA, epoxidation catalyst Ti-BEA, silylated Ti-ETS-10 11-O-04 Ti, framework, octahedral Ti-HMS 23-P-14 Ti-HMS deNOx catalyst Ti-HMS, local structure Ti-MCM-41 07-P-14 24-P-12 Ti-MCM-41 oxidation catalyst Ti-MCM-48 Ti-MFI (see TS-1) Ti-MWW TiO2, in MCM-41 TiO2, mesoporous 07-0-05 Ti-peroxo species Ti phosphates, synthesis Ti-zeolites Ti sites in TS- 1 14-P- 14 Tiling theory TI-X, exchange with In TMA-SOD Toluene adsorption Toluene, adsorption NMR, Na-X Toluene conversion, silylated MFI Toluene disproportionation 10-P-09 11-P-24 24-P-06 Toluene hydrogenation Toluene isomerisation, modelling Toluene methylation model Toluene-Na-X interaction Toluene nitration Toluene oxidation Toluene total oxidation TON catalyst TON, Fe TON, Fe, synthesis TON synthesis 02-P-22 Toxicity, clinoptilolite Toxicity, mineral dust TPD (temperature-programmed desorption) 12-P-08 13-P-10 13-P-21 26-P-22 TPD diazines/FAU TPD NH3 12-P-17 13-P-10 29-P-14 TPD-MS TPR 07-0-04 10-O-01 10-P-06 Trace elements in crop growth Transalkylation 25-0-03 Transalkylation, phenol/trimethylbenzene Transalkylation, trimethylbenzene/toluene
31-O-04 27-P-09 07-P- 17 15-P-22 26-P-22 23-P-11 14-P- 13 27-P-17 11-P-29 11-P-29 27-P-15 1 I-P- 15 29-P-08 30-P-24 30-P-24 29-P-30 29-P- 18 29-P-30 27-O-01 22-P-06 07-P-12 15-P- 18 05-0-02 27-P- 17 14-P-30 16-P- 13 09-P-10 02-P-25 18-P- 15 13-P- 16 11-O-02 29-P-26 27-0-05 15-P-20 15-O-03 13-P- 16 13-P-22 30-P-23 30-P-26 26-P- 10 04-0-04 04-0-03 04-0-04 32-P- 12 32-0-02 10-O-01 29-P-19 12-O-03 30-P-18 12-P-16 30-P-23 31-O-01 29-0-01 25-0-04 25-P-10
Transformation, hydrothermal Transformation, mesostructural Transient uptake measurement Transition energies in UV-visible Transition metal cations 04-P-11 15-P-I 1 15-P-23 Transition metal cation-modified silica Transition metal-exchanged MCM-22 Transition metal halides in porosils Transition metal incorporation Transition metal incorporation, mesoporous
02-P-36 06-P-26 19-P-08 14-O-03
27-P-08 24-P-07 30-P- 13 10-O-03 06-P- 12 silica 08-0-02 Transition metals in MCM-41 29-P-21 Transition metal mixed oxides 07-P-15 Transition metal oxide mesostructures 07-0-05 Transition metal oxides in zeolites, local structure 30-K-01 Transition metal oxides, supported catalysts 22-P-08 Transition metal-zeolite models 15-P- 13 Transition state modelling 15-P- 16 15-P- 19 Transition state selectivity 23-P-20 Tribloc copolymer surfactants 08-0-03 08-P-07 08-P-12 21-O-03 1,2,4-trichlorobenzene 23-P- 16 Trichloroethylene adsorption 18-P- 15 Trichloroethylene adsorption, MFI 17-0-02 Triethylmethylammonium in MFI 16-P-06 1,3,5-Triisopropylbenzene conversion, silylated MFI 11-O-02 1,3,5-Trisopropyibenzene cracking 29-P-07 trimetallic catalysts 30-P-22 Trimethylamine, template 09-0-03 Trimethyl benzene, swelling agent 06-P-27 1,2,4-Trimethylbenzene conversion, silylated MFI 11-O-02 Trimethylbenzene transalkylation 25-P- 10 Trimethylbenzene-phenol transalkylation 25-0-04 Trimethylpentane synthesis 24-P-20 Trimethylsilylcyanation, asymmetric 23-P-11 Tris (acetylacetonato)Cr 04-P-08 Trivalent distribution in MCM-22 14-P-21 Trivalent distribution in MFI 13-0-02 Trivalent-template interaction 13-O-01 TS-1 01-P-14 ll-P-15 27-P-11 27-P-17 TS- 1 catalyst 15-P- 18 TS-1 catalyst, effect of AI 27-0-02 TS-1, crystal morphology 06-P-25 TS- 1, framework vibrations 14-P-34 TS- 1, supported catalyst 24-P- 14 TS- 1 synthesis 14-P- 14 TS- 1 synthesis, modelling 16-P- 16 TS- 1, Ti sites 14-P- 14 14-P-30 TS- 1, water adsorption 14-P-34 Tschernichite (BEA) 0 l-K-01 Tuff, CHA, PHI-rich 31-O-01
432
Tuff, clinoptilolite-rich 0 l-P-09 22-P-12 22-P-15 31-P-11 32-P-10 Tuff, FAU-rich Tuff, montmorillonite-rich Tuff, zeolite-rich 0 I-P- 13 Tungsten carbide/FSM- 16 Tungstophosphate, Co Tunneling, proton, FAU Two-step synthesis, MSU-X
01 -P- 12 32-P-11 3 I-P-13 3 I-P-11 32-0-04 29-P-29 05-P-20 16-O-04 08-P-05
Vibrational spectroscopy, MOR 16-P-11 VOC removal 18-P-15 30-0-05 VOC removal, MCM-41 adsorbent 18-P-12 VOC deep oxidation 30-P-I 8 30-P-23 Volcano-sedimentary succession 01-O-02 Volumetric method, static 17-P-08 VPI-5 adsorbent 17-P-17 VPI-5 story PL-3 VSB-1 catalytic properties 22-0-03
W Ukraina, natural zeolites 3 l-P-08 Ultramarine, encapsulated Ultrasound monitoring, crystallisation Ultrasounds in synthesis Unit cell constant, FAU Unsaturated alcohol Unsaturated aldehydes Unsaturated ketone reduction USY (see also FAU) USY hydrotreatment catalyst USY alkylation catalyst USY polymer degradation catalyst USY, Pt,Ni isomerisation catalyst USY, treated, isomerisation catalyst USY, treated, cracking catalyst UTD-1 (DON) UTD- 1 host UV Raman spectroscopy 12-P-07 UV-Visible spectroscopy 04-P-I 1 04-P-18 10-P-08 1l-P-20 13-0-02 14-P-14 14-P-18 14-P-26 14-P-35 22-P-21 30-P-31 Vis-UV spectroscopy UV-Visible spectroscopy, models UV-Visible-NIR
3 I-P- 10 22-P- 19 02-P-37 06-P- 14 13-P-15 23-P-33 23-P-33 23-P-33 26-P-08 25-P-09 30-P-17 14-P-36 11-P-23 11-P-23 1l-P-16 10-0-03 14-P-33 lI-P-15 14-P-20 32-P-07 14-O-03 14-P-30
V V-HMS 14-P-20 V-MCM-41 oxidation catalyst 29-P- 18 V-MCM-48 06-P-06 07-P-06 V-SBA- 15, photocatalyst 24-P-07 V-Silicalites 14-P-20 Vanadium organophosphates 22-0-02 Vanadosilicate, large pore 04-0-05 Vanadosilicates, synthesis 04-0-05 Vanadyl/BEA, spectroscopic study 14-P-35 VAPO 14-P-33 VAPO-5 14-P-33 VAPO-11, synthesis 03-P-16 VAPO-41, synthesis 03-P-16 VAPSO-5 14-P-33
W,Ni/FAU hydrocracking catalyst W-based hydrotreatment catalyst Wall properties, mesoporous silica Wall structure, mesoporous silica Wall structure, SBA- 15 Washing, effect on MCM-41 Waste streams, nuclear industry Wastewater treatment 3 l-P-14 Wastewater, agroindustrial Wastewater, Cr removal Wastewater, nitrogen industry Wastewater, Pb removal Wastewater, petroleum refineries Water adsorption models Water adsorption, TS- 1 Water adsorption, AIMepO Water clusters in FAU Water desorption from LTA Water desorption, modified MCM-41 Water diffusion, simulation Water, drinking, deammoniation Water effect on adsorption 16-O-03 19-P-06 Water, effect on NOx storage Water rolling Water storage Water treatment, fisheries WS2 HDS catalyst
1 l-P-08
26-P-08 08-P-14 06-P-05 08-0-03 06-P-28 05-O-01 31-P-15 31-0-03 31-P-13 31-P-10 3 I-P-06 30-P-20 16-O-03 14-P-34 09-P- 14 15-0-04 17-P-09 17-P-13 15-P-28 3 I-P-09 32-P-08 30-0-04 15-P-28 31-O-04 31 -P- 12 26-P- 17
X XAFS measurement 14-P-20 14-P-26 XAFS, Fe ZSM-5 XANES 14-P-08 129Xe-NMR, chemical shift 129Xe NMR in diffusion studies 129Xe NMR, MCM-48 131Xe-NMR, chemical shift Xe-SF6 diffusion in BOG, modelling XPS 04-P-18 09-P-10 26-P-14 XPS, Co XPS, Cu in MFI
28-P-07 12-O-02 14-P-39 14-P-27 19-P-09 06-P- 16 14-P-27 16-O-05 30-P-26 04-P- 18 30-P-21
433
X-ray diffraction X-ray diffraction, Ag-clinoptilolite X-ray diffraction, chloroalkene adsorption X-ray diffraction, grazing incidence X-ray diffraction, mesoporous silica X-ray diffraction, temperature resolved X-ray powder refinement X-ray scattering, mesoporous silica Xylene adsorption models m-Xylene conversion 12-P-14 Xylene isomerisation Xylene isomerisation, modelling Xylene isomerisation, NMR Xylene production Xylene separation Xylene separation, affected by water
05-0-04 01-P-15 17-P-11 20-0-04 06-P-05 09-P-13 09-P-07 06-P-05 16-O-03 26-P-20 28-P-06 15-P-20 12-0-01 25-P-10 18-P-08 16-O-03
Z Zearalenone, adsorption Zeolite A, s e e LTA Zeolite adsorbents, from fly ash Zeolite Beta, s e e BEA Zeolite F (EDI) synthesis, role of K and Na Zeolite modification Zeolite P (GIS) Zeolite X, s e e FAU Zeolite Y, s e e FAU Zeolitisation, bentonite in sea water Zeolitisation, diatoms Zeolitisation of volcanic glass Zeolitisation, volcano-sedimentary Zeoponic fertilizer delivery ZK-21, Ca form (LTA) ZK-21, Na,TMA (LTA) ZK-5, rare earth ZK-5, synthesis Zn-alumina, mesoporous ZnAPO-31 ZnAPO-37 Zn-FAU 10-P-05 Zn-LTA Zn-MFI Zn-MFI, sulfide host Zn-MFI, synthesis Zn-MOR 04-P-15 Zn,Ni-MFI, aromatisation catalyst 24-P-30 24-P-31 Zn phosphates Zn phosphate catalysts Zn spinel from zeolites ZnO clusters ZnO-CuO-ZrO2 Zn-Pt/zeolite X Zn-zeolites, oxidation catalyst
32-0-04 18-P- 10 03-0-05 3 l-P-08 3 I-P-05
03-P-06 2 l-P-07 0 I-P-I 3 01-O-02 31-O-02 18-P-13 18-P-13 I l-P-19 02-P-21 07-P- 16 14-P- 13 29-P-23 17-P-14 10-P-05 24-P-27 29-P-05 04-P- 14 13-P-32 28-0-02 05-0-04 29-P-23 10-P-07 10-P-05 24-P-26 29-P- 15 27-P-08
Zorite Zr/AI-MCM-41 Zr/AI-MCM-41, synthesis Zr-ETS-4 Zr-HMS, hydrotreatment catalyst Zr-HMS, support Zr-MCM-41 as Ni support Zr-MCM-41 oxidation catalyst ZrO2-CuO-ZnO ZrO2 derivatives ZrO2 nanoparticles in SBA-15 ZrO2 mesoporous 07-P-090 ZrO2/Na-Y ZrO2, Ni fuel cell catalyst ZrO2/SO42" ZSM-5, s e e MFI ZSM-12, s e e MTW ZSM-20 (FAU-EMT intergrowth) ZSM-22, s e e TON ZSM-25, synthesis ZSM-34 (ERI/OFF), synthesis ZSM-35 (FER) catalyst ZSM-48, synthesis
1 l-P-15
16-P-19 29-P-24 04-P- 16 26-P-22 26-P-22 23-P-28 29-P-18 24-P-26 07-P-09 29-P-17 7-P-I 1 07-P-20 30-P-08 07-P-20 29-P-07
13-P-21 02-P-10 02-P-22 26-P-10 02-P-41
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STUDIES IN SURFACE SClENCEAND CATALYSIS Advisory Editors: B. Delmon, Universitd Catholique de Louvain, Louvain-la-Neuve, Belgium J.T.Yates, University of Pittsburgh, Pittsburgh, PA, U.S.A. Volume 1
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Preparation of Catalysts I.Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedings of the First International Symposium, Brussels, October 14-17,1975 edited by B. Delmon, RA. Jacobs and G. Poncelet The Control of the Reactivity of Solids. A Critical Survey of the Factors that Influence the Reactivity of Solids, with Special Emphasis on the Control of the Chemical Processes in Relation to Practical Applications by V.V. Boldyrev, M. Bulens and B. Delmon Preparation of Catalysts II. Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedingsofthe Second International Symposium, Louvain-la-Neuve, September 4-7, 1978 edited by B. Delmon, R Grange, R Jacobs and G. Poncelet Growth and Properties of Metal Clusters. Applications to Catalysis and the Photographic Process. Proceedings of the 32nd International Meeting of the Soci6td de Chimie Physique, Villeurbanne, September 24-28,1979 edited by J. Bourdon Catalysis by Zeolites. Proceedings of an International Symposium, Ecully (Lyon), September 9-11,1980 edited by B. Imelik, C. Neccache,Y. BenTaadt, J.C.Veddne, G. Coududer and H. Praliaud Catalyst Deactivation. Proceedings of an International Symposium, Antwerp, October 13-15,1980 edited by B. Delmon and G.E Froment New Hodzons in Catalysis. Proceedings of the 7th International Congress on Catalysis,Tokyo, June 30-July4, 1980. PartsA and B edited by 1".Seiyama and K.Tanabe Catalysis by Supported Complexes by Yu.I.Yermakov, B.N. Kuznetsov andV.A. Zakharov Physics of Solid Surfaces. Proceedings of a Symposium, Bechy~e, September 29-October 3,1980 edited by M. L6zni~,ka Adsorption at the Gas-Solid and Liquid-Solid Interface. Proceedings of an International Symposium, Aix-en-Provence, September 21-23,1981 edited by J. Rouquerol and K.S.W. Sing Metal-Support and Metal-Additive Effects in Catalysis. Proceedings of an International Symposium, Ecully (Lyon), September 14-16,1982 edited by B. Imelik, C. Naccache, G. Coududer, H. Preliaud, R Medaudeau, R Gallezot, G.A. Martin and J.C.Veddne Metal Microstructures in Zeolites. Preparation - Properties-Applications. Proceedings of aWorkshop, Bremen, September 22-24, 1982 edited by RA. Jacobs, N.I. Jaeger, R Jid= and G. Schulz-Ekloff Adsorption on Metal Surfaces. An Integrated Approach edited by J. B6nard Vibrations at Surfaces. Proceedings of theThird International Conference, Asilomar, CA, September 1-4,1982 edited by C.R. Brundle and H. Morawitz Heterogeneous Catalytic Reactions Involving Molecular Oxygen by G.I. Golodets
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Volume 17 Volume 18 Volume 19 Volume 20 Volume 21 Volume 22 Volume 23 Volume 24 Volume 25 Volume 26 Volume 27 Volume 28 Volume 29 Volume 30 Volume 31
Volume 32 Volume 33 Volume 34 Volume 35
Preparation of Catalysts Ul. Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedings oftheThird International Symposium, Louvain-la-Neuve, September 6-9, 1982 edited by G. Poncelet, R Grange and RA. Jacobs Spillover of Adsorbed Species. Proceedings of an International Symposium, Lyon-Villeurbanne, September 12-16,1983 edited by G.M. Pajonk, S.J.Teichner and J.E. Germain Structure and Reactivity of Modified Zeolites. Proceedings of an International Conference, Prague, July 9-13,1984 edited by RA. Jacobs, N.I. Jaeger, R Ji~,V.B. Kazansky and G. Schulz-Ekloff Catalysis on the Energy Scene. Proceedings of the 9th Canadian Symposium on Catalysis, Quebec, RQ., September 30-October 3,1984 edited by S. Kaliaguine andA. Mahay Catalysis by Acids and Bases. Proceedings of an International Symposium, Villeurbanne (Lyon), September 25-27,1984 edited by B. Imelik, C. Naccache, G. Coud.uder,Y. BenTaadt and J.C.Veddne Adsorption and Catalysis on Oxide Surfaces. Proceedings of a Symposium, Uxbridge, June 28-29,1984 edited by M. Che and G.C. Bond Unsteady Processes in Catalytic Reactors by Yu.Sh. Matros Physics of Solid Surfaces 1984 edited by J. Koukal Zeolites: Synthesis, Structure,Technology and Application. Proceedings of an International Symposium, Portoroi-Portorose, September 3-8,1984 edited by B. Dr~aj, S. Ho(:evar and S. Pejovnik Catalytic Polymerization of Olefins. Proceedings of the International Symposium on Future Aspects of Olefin Polymerization,Tokyo, July 4-6,1985 edited by T. Keii and K. Soga Vibrations at Surfaces 1985. Proceedings of the Fourth International Conference, Bowness-on-Windermere, September 15-19,1985 edited by D.A. King, N.V. Richardson and S. Holloway Catalytic Hydrogenation edited by L. Cerven~ New Developments in Zeolite Science andTechnology. Proceedings of the 7th International Zeolite Conference,Tokyo, August 17-22,1986 edited by Y. Murakami, A. lijima and J.W.Ward Metal Clusters in Catalysis edited by B.C. Gates, L. Guczi and H. Kn6zinger Catalysis andAutomotive Pollution Control. Proceedings of the First International Symposium, Brussels, September 8-11,1986 edited by A. Crucq andA. Frennet Preparation of Catalysts IV. Scientific Basesfor the Preparation of Heterogeneous Catalysts. Proceedings of the Fourth International Symposium, Louvain-laNeuve, September 1-4,1986 edited by B. Delmon, R Grange, RA. Jacobs and G. Poncelet Thin Metal Films and Gas Chemisorption edited by RWissmann Synthesis of High-silicaAluminosilicate Zeolites edited by RA. Jacobs and J.A. Martens Catalyst Deactivation 1987. Proceedings of the 4th International Symposium, Antwerp, September 29-October 1,1987 edited by B. Delmon and G.E Froment Keynotes in Energy-Related Catalysis edited by S. Kaliaguine
437 Volume 36 Volume 37 Volume 38 Volume 39 Volume 40 Volume 41
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Volume 45 Volume 46
Volume 47 Volume 48 Volume 49 Volume 50
Volume 51 Volume 52 Volume 53 Volume 54
Methane Conversion. Proceedings of a Symposium on the Production of Fuels and Chemicals from Natural Gas,Auckland, April 27-30, 1987 edited by D.M. Bibby, C.D. Chang, R.E Howe and S.Yurchak Innovation in Zeolite Materials Science. Proceedings of an International Symposium, Nieuwpoort, September 13-17,1987 edited by RJ. Grobet, W.J. Mortier, E.EVansant and G. Schulz-Ekloff Catalysis 1987.Proceedings ofthe 10th North American Meeting ofthe Catalysis Society, San Diego, CA, May 17-22,1987 edited by J.W.Ward Characterization of Porous Solids. Proceedings of the IUPAC Symposium (COPS I), Bad Soden a.Ts.,Apri126-29,1987 edited by K.K. Unger, J. Rouquerol, K.S.W. Sing and H. Kral Physics of Solid Surfaces 1987. Proceedings of the Fourth Symposium on Surface Physics, Bechyne Castle, September 7-11,1987 edited by J. Koukal Heterogeneous Catalysis and Fine Chemicals. Proceedings of an International Symposium, Poitiers, March 15-17,1988 edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier and G. P6rot Laboratory Studies of Heterogeneous Catalytic Processes by E.G. Chdstoffel, revised and edited by Z. Pa61 Catalytic Processes under Unsteady-State Conditions by Yu. Sh. Matros Successful Design of Catalysts. Future Requirements and Development. Proceedings 0ftheWorldwide Catalysis Seminars, July, 1988, on the Occasion of the 30th Anniversary of the Catalysis Society of Japan edited by T. Inui Transition Metal Oxides. Surface Chemistry and Catalysis by H.H. Kung Zeolites as Catalysts, Sorbents and Detergent Builders. Applications and Innovations. Proceedings of an International Symposium,W~irzburg, September 4--8,1988 edited by H.G. Karge and J.Weitkamp Photochemistry on Solid Surfaces edited by M.Anpo andT. Matsuura Structure and Reactivity of Surfaces. Proceedings of a European Conference, Trieste, September 13-16,1988 edited by C. Morterra,A. Zecchina and G. Costa Zeolites: Facts, Figures, Future. Proceedings of the 8th International Zeolite Conference, Amsterdam, July 10-14,1989. Parts A and B edited by P.A.Jacobs and R.A. van Santen Hydrotreating Catalysts. Preparation, Characterization and Performance. Proceedings of the Annual International AIChE Meeting,Washington, DC, November 27-December 2,1988 edited by M.L. Occelli and R.G.Anthony New Solid Acids and Bases.Their Catalytic Properties by K.Tanabe, M. Misono,Y. Ono and H. Hattori RecentAdvances in Zeolite Science. Proceedings of the 1989 Meeting of the British Zeolite Association, Cambridge, April 17-19,1989 edited by J. Klinowsky and RJ. Barrie Catalyst in Petroleum Refining 1989. Proceedings of the First International Conference on Catalysts in Petroleum Refining, Kuwait, March 5-8,1989 edited by D.L.Tdmm,S.Akashah, M.Absi-Halabi andA. Bishara Future Opportunities in Catalytic and Separation Technology edited by M. Misono, Y. Moro-oka and S. Kimura
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New Developments in Selective Oxidation. Proceedings of an International Symposium, Rimini, Italy, September 18-22,1989 edited by G. Centi and I-.Tdfiro Volume 56 Olefin Polymerization Catalysts. Proceedings of the International Symposium on Recent Developments in Olefin Polymerization Catalysts,Tokyo, October 23-25,1989 edited by T. Keii and K. Soga Volume 57A SpectroscopicAnalysis of Heterogeneous Catalysts. Part A: Methods of SurfaceAnalysis edited by J.L.G. Fiewo Volume 57B SpectroscopicAnalysis of Heterogeneous Catalysts. Part B: Chemisorption of Probe Molecules edited by J.L.G. Fierro Introduction to Zeolite Science and Practice Volume 58 edited by H. van Bekkum, E.M. Flanigen and J.C. Jansen Volume 59 Heterogeneous Catalysis and Fine C.hemicals II. Proceedings of the 2nd International Symposium, Poitiers, October 2-6,1990 edited by M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, G. P6rot, R. Maurel and C. Montassier Volume 60 Chemistry of Microporous Crystals. Proceedings of the International Symposium on Chemistry of Microporous Crystals,Tokyo, June 26-29,1990 edited by T. Inui, S. Namba andT.Tatsumi Volume 61 Natural Gas Conversion. Proceedings of the Symposium on Natural Gas Conversion, Oslo, August 12-17,1990 edited by A. Holmen, K.-J. Jens and S. Kolboe Volume 62 Characterization of Porous Solidsll. Proceedings of the IUPAC Symposium (COPS II),Alicante, May 6-9,1990 edited by F.Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing and K.K. Unger Volume 63 Preparation of CatalystsV. Scientific Bases for the Preparation of Heterogeneous Catalysts. Proceedings of the Fifth International Symposium, Louvain-la-Neuve, September 3-6,1990 edited by G. Poncelet, P.A.Jacobs, P.Grange and B. Delmon Volume 64 NewTrends in COActivation edited by L. Guczi Volume 65 Catalysis and Adsorption by Zeolites. Proceedings of ZEOCAT 90, Leipzig, August 20-23,1990 edited by G. ~hlmann, H. Pfeifer and R. Fdcke Volume 66 Dioxygen Activation and Homogeneous Catalytic Oxidation. Proceedings of the Fourth International Symposium on Dioxygen Activation and Homogeneous Catalytic Oxidation, Balatonf(ired, September 10-14,1990 edited by L.I. Sim~ndi Volume 67 Structure-Activity and Selectivity Relationships in Heterogeneous Catalysis. Proceedings of the ACS Symposium on Structure-Activity Relationships in Heterogeneous Catalysis, Boston, MA, Apri122-27, 1990 edited by R.K. GrasseUi andA.W. Sleight Volume 68 Catalyst Deactivation 1991. Proceedings of the Fifth International Symposium, Evanston, IL, June 24-26,1991 edited by C.H. Bartholomew and J.B. Butt Volume 69 Zeolite Chemistry and Catalysis. Proceedings of an International Symposium, Prague, Czechoslovakia, September 8-13, 1991 edited by RA. Jacobs, N.I. Jaeger, L. Kubelkov6 and B.Wichtedov6 Volume 70 Poisoning and Promotion in Catalysis based on Surface Science Concepts and Experiments by M. Kiskinova
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Volume 79 Volume 80 Volume81 Volume 82
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Volume 85 Volume 86 Volume 87
Catalysis and Automotive Pollution Control II. Proceedings of the 2nd International Symposium (CAPoC 2), Brussels, Belgium, September 10-13,1990 edited by A. Crucq New Developments in Selective Oxidation by Heterogeneous Catalysis. Proceedings of the 3rd European Workshop Meeting on New Developments in Selective Oxidation by Heterogeneous Catalysis, Louvain-la-Neuve, Belgium, April 8-10,1991 edited by R Ruiz and B. Delmon Progress in Catalysis. Proceedings of the 12th Canadian Symposium on Catalysis, Banff, Alberta, Canada, May 25-28, 1992 edited by K.J. Smith and E.C.Sanford Angle-Resolved Photoemission.Theory and CurrentApplications edited by S.D. Kevan New Frontiers in Catalysis, PartsA-C. Proceedings of the 10th International Congress on Catalysis, Budapest, Hungary, 19-24 July, 1992 edited by L. Guczi, F.Solymosi a~d RT6t6nyi fluid Catalytic Cracking: Science andTechnology edited by J.S. Magee and M.M. Mitchell, Jr. NewAspects of Spillover Effect in Catalysis. For Development of HighlyActive Catalysts. Proceedings of theThird International Conference on Spillover, Kyoto, Japan,August 17-20,1993 edited by T. Inui, K. Fujimoto,T. Uchijima and M. Masai Heterogeneous Catalysis and Fine Chemicals III. Proceedings of the 3rd International Symposium, Poitiers, April 5 - 8,1993 edited by M. Guisnet, J. Barbier, J. Barrault, C. Bouchoule, D. Duprez, G. P6rot and C. Montassier Catalysis: An Integrated Approach to Homogeneous, Heterogeneous and Industrial Catalysis edited by J.A. Moulijn, RW.N.M. van Leeuwen and R.A. van Santen Fundament=_!s of Adsorption. Proceedings of the Fourth International Conference on Fundamentals ofAdsorption, Kyoto, Japan, May 17-22,1992 edited by M. Suzuki Natural Gas Conversion ~.. Proceedings of theThird Natural Gas Conversion Symposium, Sydney, July 4-9,1993 edited by H.E. Curry-Hyde and R.F.Howe New Developments in Selective Oxidation II. Proceedings of the SecondWorld Congress and Fourth EuropeanWorkshop Meeting, Benalmddena, Spain, September 20-24,1993 edited by V. Cort6s Corber6n and S.Vic Bell6n Zeolites and Microporous Crystals. Proceedings of the International Symposium on Zeolites and Microporous Crystals, Nagoya, Japan,August 22-25,1993 edited byT. Hattod andT.Yashima Zeolites and Related Microporous Materials: State of theArt 1994. Proceedings of the 10th International Zeolite Conference, Garmisch-Partenkirchen, Germany, July 17-22,1994 edited by J.Weitkamp, H.G. Karge, H. Pfeifer andW. H61dedch Advanced Zeolite Science and Applications edited by J.C. Jansen, M. St6cker, H.G. Karge and J.Weitkamp Oscillating Heterogeneous Catalytic Systems by M.M. Slin'ko and N.I. Jaeger Characterization of Porous Solids Ul. Proceedings of the IUPAC Symposium (COPS III), Marseille, France, May 9-12,1993 edited by J.Rouquerol, F.Rodriguez-Reinoso, K.S.W. Sing and K.K. Unger
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Volume 93 Volume 94 Volume95 Volume 96
Volume97 Volume 98
Volume 99 Volume 100
Volume 101 Volume 102 Volume 103 Volume 104 Volume 105
Catalyst Deactivation 1994. Proceedings of the 6th International Symposium, Ostend, Belgium, October 3-5,1994 edited by B. Delmon and G.E Froment Catalyst Design forTailor-made Polyolefins. Proceedings of the International Symposium on Catalyst Design forTailor-made Polyolefins, Kanazawa, Japan, March 10-12,1994 edited by K. Soga and M.Terano Acid-Base Catalysis II. Proceedings of the International Symposium on Acid-Base Catalysis II, Sapporo, Japan, December 2-4,1993 edited by H. Hattori, M. Misono andY. Ono Preparation of CatalystsVI. Scientific Bases for the Preparation of Heterogeneous Catalysts. Proceedings of the Sixth International Symposium, Louvain-La-Neuve, September 5-8,1994 edited by G. Poncelet, J. Martens, B. Delmon, RA. Jacobs and R Grange Science andTechnology in Catalysis 1994. Proceedings of the SecondTokyo Conference on Advanced Catalytic Science andTechnology, Tokyo, August 21-26,1994 edited by Y. Izumi, H.Arai and M. Iwamoto Charactedzation and Chemical Modification of the Silica Surface by E.EVansant, RVan DerVoort and K.C.Vrancken Catalysis by Microporous Matedals. Proceedings of ZEOCAT'95, Szombathely, Hungary, July 9-13,1995 edited by H.K. Beyer, H.G.Karge, I. Kiricsi and J.B. Nagy Catalysis by Metals andAIIoys by V. Ponec and G.C. Bond Catalysis and Automotive Pollution Control III. Proceedings of theThird International Symposium (CAPoC3), Brussels, Belgium, April 20-22,1994 edited by A. Frennet and J.-M. Bastin Zeolites:A RefinedTool for Designing Catalytic Sites. Proceedings of the International Symposium, Qu6bec, Canada, October 15-20,1995 edited by L. Bonneviot and S. Kaliaguine Zeolite Science 1994: Recent Progress and Discussions. Supplementary Materials to the 10th International Zeolite Conference, Garmisch-Partenkirchen, Germany, July 17-22,1994 edited by H.G. Karge and J.Weitkamp Adsorption on New and Modified Inorganic Sorbents edited by A. Dqbrowski andV.A.Tertykh Catalysts in Petroleum Refining and Petrochemical Industdes 1995. Proceedings ofthe 2nd International Conference on Catalysts in Petroleum Refining and Petrochemical Industries, Kuwait, April 22-26,1995 edited by M.Absi-Halabi, J. Beshara, H. Qabazard andA. Stanislaus 11th International Congress on Catalysis - 40th Anniversary. Proceedings ofthe 11th ICC, Baltimore, MD, USA, June 30-July 5,1996 edited by J.W. Hightower, W.N. Delgass, E. Iglesia andA.T. Bell RecentAdvances and New Hodzons in Zeolite Science andTechnology edited by H. Chon, S.I.Woo and S.-E. Park Semiconductor Nanoclusters - Physical, Chemical, and CatalyticAspects edited by RV. Kamat and D. Meisel Equilibda and Dynamics of GasAdsorption on Heterogeneous Solid Surfaces edited by W. Rudzir~ski,W.A. Steele and G. Zgrablich Progress in Zeolite and Microporous Matedals Proceedings of the 11th International Zeolite Conference, Seoui, Korea, August 12-17,1996 edited by H. Chon, S.-K. Ihm andY.S. Uh
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Volume 111 Volume 112
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Volume 115 Volume 116
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Volume 119
Hydrotreatment and Hydrocracking of Oil Fractions Proceedings of the 1st International Symposium / 6th EuropeanWorkshop, Oostende, Belgium, February 17-19,1997 edited by G.F. Froment, B. Delmon and R Grange Natural Gas Conversion IV Proceedings of the 4th International Natural Gas Conversion Symposium, Kruger Park, South Africa, November 19-23,1995 edited by M. de Pontes, R.L. Espinoza, C.R Nicolaides, J.H. Scholtz and M.S. Scurrell Heterogeneous Catalysis and Fine Chemicals IV Proceedings of the 4th International Symposium on Heterogeneous Catalysis and Fine Chemicals, Basel, Switzerland, September 8-12,1996 edited by H.U. Blaser,A. Balker and R. Pdns Dynamics of Surfaces and Reaction Kinetics in Heterogeneous Catalysis. Proceedings of the International Symposium,Antwerp, Belgium, September 15-17,1997 edited by G.F. Froment and K.C.Waugh ThirdWorld Congress on Oxidation Catalysis. Proceedings of theThirdWorld Congress on Oxidation Catalysis, San Diego, CA, U.S.A., 21-26 September 1997 edited by R.K. Grasselli, S.T. Oyama, A.M. Gaffney and J.E. Lyons Catalyst Deactivation 1997. Proceedings of the 7th International Symposium, Cancun, Mexico, October 5-8,1997 edited by C.H. Bartholomew and G.A. Fuentes Spillover and Migration of Surface Species on Catalysts. Proceedings ofthe 4th International Conference on Spillover, Dalian, China, September 15-18,1997 edited by Can Li and Qin Xin RecentAdvances in Basic and Applied Aspects of Industrial Catalysis. Proceedings ofthe 13th National Symposium and Silver Jubilee Symposium of Catalysis of India, Dehradun, India, April 2-4,1997 edited by T.S.R. Prasada Rao and G. Murali Dhar Advances in Chemical Conversions for Mitigating Carbon Dioxide. Proceedings of the 4th International Conference on Carbon Dioxide Utilization, Kyoto, Japan, September 7-11,1997 edited by T. Inui, M.Anpo, K. Izui, S.Yanagida andT.Yamaguchi Methods for Monitoring and Diagnosing the Efficiency of Catalytic Converters. A patent-oriented survey by M. Sideris Catalysis and Automotive Pollution Control IV. Proceedings of the 4th International Symposium (CAPoC4), Brussels, Belgium, April 9-11,1997 edited by N. Kruse, A. Frennet and J.-M. Bastin Mesoporous Molecular Sieves 1998 Proceedings of the 1st International Symposium, Baltimore, MD, U.S.A., July 10-12,1998 edited by L.Bonneviot, E B61and,C. Danumah, S. Giasson and S. Kaliaguine Preparation of Catalysts VII Proceedings ofthe 7th International Symposium on Scientific Bases for the Preparation of Heterogeneous Catalysts, Louvain-la-Neuve, Belgium, September 1-4,1998 edited by B. Delmon, RA. Jacobs, R. Maggi, J.A. Martens, R Grange and G. Poncelet Natural Gas ConversionV Proceedings of the 5th International Gas Conversion Symposium, Giardini-Naxos, Taormina, Italy, September 20-25,1998 edited by A. Parmaliana, D. Sanfilippo, E Frusted,A.Vaccad and F.Arena
442 Volume 120A Adsorption and its Applications in Industry and Environmental Protection. Vol I: Applications in Industry edited by A. D0browski Volume 120B Adsorption and its Applications in Industry and Environmental Protection. Vol I1:Applications in Environmental Protection edited byA. Dsbrowski Volume 121 Science andTechnology in Catalysis 1998 Proceedings of theThirdTokyo Conference in Advanced Catalytic Science and Technology,Tokyo, July 19-24,1998 edited by H. Hattori and K. Otsuka Volume 122 Reaction Kinetics and the Development of Catalytic Processes Proceedings ofthe International Symposium, Brugge, Belgium, April 19-21,1999 edited by G.E Froment and K.C.Waugh Volume 123 Catalysis: An Integrated Approach Second, Revised and Enlarged Edition edited by R.A. van Santen, RW.N.M. van Leeuwen, J.A. Moulijn and B.A.Averill Volume 124 Experiments in Catalytic Reaction Engineering by J.M. Berry Volume 125 Porous Materials in Environmentally Friendly Processes Proceedings ofthe 1st International FEZA Conference, Eger, Hungary, September 1-4,1999 edited by I. Kiricsi, G. P=tl-Borb61y,J.B. Nagy and H.G. Karge Volume 126 Catalyst Deactivation 1999 Proceedings of the 8th International Symposium, Brugge, Belgium, October 10-13,1999 edited by B. Delmon andG.E Froment Volume 127 Hydrotreatment and Hydrocracking of Oil Fractions Proceedings of the 2nd International Symposium/7th European Workshop, Antwerpen, Belgium, November 14-17,1999' edited by B. Delmon, G.E Froment and R Grange Volume 128 Characterisation of Porous SolidsV Proceedings of the 5th International Symposium on the Characterisation of Porous Solids (COPS-V), Heidelberg, Germany, May 30- June 2,1999 edited by K.K. Unger, G. Kreysa and J.R Baselt Volume 129 Nanoporous Materials II Proceedings of the 2nd Conference on Access in Nanoporous Materials, Banff, Alberta, Canada, May 25-30, 2000 edited byA. Sayari, M. Jaronier andT.J. Pinnavaia Volume 130 12th Intemational Congress on Catalysis Proceedings of the 12th ICC, Granada, Spain, July 9-14, 2000 edited byA. Corma, EV. Melo, S. Mendioroz and J.L.G. Fierro Volume 131 Catalytic Polymerization of Cycloolefins Ionic, Ziegler-Natta and Ring-Opening Metathesis Polymerization byV. Dragutan and R. Streck Volume 132 Proceedings of the Intemational Conference on Colloid and Surface Science, Tokyo, Japan, November 5-8, 2000 25th Anniversary ofthe Division of Colloid and Surface Chemistry, The Chemical Society of Japan edited byY. Iwasawa, N. Oyama and H. Kunieda Volume 133 Reaction Kinetics and the Development and Operation of Catalytic Processes Proceedings of the 3rd International Symposium, Oostende, Belgium, April 22-25, 2001 edited by G.E Froment and K.C.Waugh Volume 134 Fluid Catalytic CrackingV Materials and Technological Innovations edited by M.L. Occelli and R O'Connor
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Zeolites and Mesoporous Materials at the Dawn of the 21st Century. Proceedings of the 13th International Zeolite Conference, Montpellier, France, 8-13 July 2001 edited by A. Galameau, E di Renzo, E Fajula and J.Vedrine
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