Nanochemistry

Contents Foreword

vii ix

Introduction

1

1

Survey of the Problem and Certain Definitions

2

Synthesis and Stabilization of Nanoparticles 2.1 C h e m i c a l Reduction 2.2 Reactions in Micelles, Emulsions, and Dendrimers 2.3 Photochemical and Radiation C h e m i c a l Reduction 2.4 C r y o c h e m i c a l Synthesis 2.5 Physical Methods 2.6 Particles of Various Shapes and F i l m s

7 8 12 16 20 30 32

3

Experimental Techniques 3.1 Electron M i c r o s c o p y 3.1.1 Transmission electron microscopy 3.1.2 Scanning electron microscopy 3.2 Probe M i c r o s c o p y 3.3 Diffraction Techniques 3.3.1 X - r a y diffraction 3.3.2 Neutron diffraction 3.4 Miscellaneous Techniques 3.4.1 E X A F S 3.4.2 X - r a y fluorescence spectroscopy 3.4.3 M a s s spectrometry 3.4.4 Photoelectron spectroscopy 3.5 Comparison of Spectral Techniques Used for Elemental Analysis

37 38 38 38 39 42 42 43 43 43 43 44 44 44

4

Cryochemistry of Metal Atoms and Nanoparticles 4.1 Reactions of M a g n e s i u m Particles 4.1.1 Grignard reactions 4.1.2 Activation of small molecules 4.1.3 Explosive reactions 4.2 Silver and Other Metals 4.2.1 Stabilization by polymers 4.2.2 Stabilization by mesogenes 4.3 Reactions of Rare-Earth Elements 4.4 Activity, Selectivity, and Size Effects 4.4.1 Reactions at superlow temperatures 4.4.2 Reactions of silver particles of various sizes and shapes

47 47 47 51 53 57 57 65 69 75 75 83

xi

Xll

4.5

Theoretical Methods 4.5.1 General remarks 4.5.2 Simulation of the structure of mixed metallic particles 4.5.3 Simulation of properties of intercalation compounds 4.5.4 Simulation of structural elements of organometallic co-condensates

87 87 89 92 94

5

Chemical Nanoreactors 5.1 General Remarks 5.2 A l k a l i and A l k a l i - E a r t h Elements 5.3 Transition Metals of Groups I I I - V I I i n the Periodic Table 5.4 Elements of the group V I I I of the Periodic System 5.5 Subgroups of Copper and Z i n c 5.6 Subgroup of B o r o n and Arsenic 5.7 Assemblies Involving Nanoparticles

99 99 103 112 121 131 137 141

6

Group of Carbon 6.1 Fine Particles of Carbon and Silicon 6.2 Fullerenes 6.3 Carbon Nanotubes 6.3.1 F i l l i n g of tubes 6.3.2 Grafting of functional groups. Tubes as matrices 6.3.3 Intercalation of atoms and molecules into multi-walled tubes

147 147 148 150 151 152 154

7

Size 7.1 7.2 7.3 7.4

Effects in Nanochemistry M o d e l s of Reactions of M e t a l A t o m s in Matrices M e l t i n g Point Optical Spectra Kinetic Peculiarities of C h e m i c a l Processes on the Surface of Nanoparticles 7.5 Thermodynamic Features of Nanoparticles

157 157 159 162

Nanoparticles in Science and Technology 8.1 Catalysis on Nanoparticles 8.2 O x i d e Reactions 8.3 Semiconductors, Sensors, and Electronic Devices 8.4 Photochemistry and Nanophotonics 8.5 Applications of C N T s 8.6 Nanochemistry in B i o l o g y and M e d i c i n e

175 175 184 188 197 199 202

8

168 170

Conclusion

209

References

215

Subject Index

247

Index ab initio methods 88-89, 93 activation of small molecules 51-53 aerosol techniques 22 aggregation of silver particles 17 A u - A g alloy 14 aluminum particles and reactions 139-140 analysis of spectral techniques 45 atomic-force microscopy 41-42, 60, 101, 142, 144 bimetallic Pd-Rh particles Ag-Pb particles 62 A u - N i particles 19 Au-Pd particles 19 Fe-Pt particles 130 Pd-Au particles 14, 18 Pd-Rh particles 14 biomolecules 13, 124, 130, 193, 203-207 bismuth particles 12 calcium particles, reactions 79, 107-108 carbon nanotubes applications 155 filling 85, 151-152, 201-202 grafting 152-153, 166 intercalation 92, 151, 154-155 catalysis bimetallic Pt-Au 177 gold nanoparticle 204 influence of particle size 182 nanopens 180 palladium nanoparticles 175, 184 T i 0 2 and Ag-Ti0 2 , 179 CdSe particles 142, 189 chemical reduction 8-10, 16-18 chromium particles 120 cobalt particles 10, 128 reactions 10 co-condensates silver cyanobiphenyl 66 complex of D N A and CdSe 204 copper particles 10, 13, 28, 33, 133, 135, 154 core-ligand complex 103

core-shell A g - A u particles 14 CdS-ZnS 188 Co-CdSe 130 FePt-Fe 3 0 4 131 Pd-Pt, Pd-Au, Pd-Rh 14 core-shell particles, structures 12, 14-15, 35, 129, 143 critical film thickness 55 cryochemical synthesis 20-29 dendrimers 12-15 destruction of carbon tetrachloride 53 diffraction techniques 37, 42-43, 144 drug modification 206 dynamic light scattering techniques 63 electric explosion techniques 136 electrochemical dissolution 10 electron microscopy 19, 33-34, 36, 38-39, 144 electronic circuit 191 noses 196 EPR method 66 E X A F S 38, 43, 101 exchange reactions, kinetics 169 explosive reactions 53-56 fast crystallization 6 films, conductivity 62-63 fullerenes 148-151, 154 GaPnanowires 189 germanium particles 120 gold films 143-144 nanoshells 136 optical properties 198 particles 5, 8-9, 14, 17-18, 120, 133, 135-137, 141-144, 159, 170, 173, 176-177, 188-189, 193, 198, 203-204, 206 Grignard reactions 47-50

helium nanodroplets 30 heterodimers 12, 124 heterogeneous films 35 hexogen nanoparticles 30 hollow structures 13 hybrid nanomaterials 120, 196 hydrocarbons chlorination 109 indium films 160 particles 161 indium nitride nanowires 140 ionization potential 106 iron complexes 127 particles 122-123, 127 reactions 122-123 kinetic nanoparticles 168-170, 197 Knudsen cells 21-22 lead clusters 57 lithium oxide 187 particles 93 magnesium atoms 77-79, 82 particles 4 7 - 5 6 reactions 4 7 - 5 6 mass spectrometry 44 matrix-isolation method 80 metal oxides nanoporous 16 metal-containing polymers 13 metal-nonmetal transition 5 M g - C 0 2 complex, ab initio calculations 78 molybdenum particles 116 sulfide particles 180 nanobelts 35, 195 nanochemistry definition 5 nanocomposites, definition 2 nanoparticles classifications 2 nanorattles 137

nanoribbons 35, 136 nanorods 187-188, 190 nanostructure definition 2 nanotubes A 1 N , G a N 35 FePb, F e 3 0 4 35 N b S e 2 190 nanowires 133 neutron diffraction 43 nickel particles 33, 124, 182 reaction 128 niobium particles and reactions 115-118 oxide reactions 184-187 oxide, magnesium, absorption 104 oxides 11 palladium nanowires 131 particles 18, 33, 121, 184 particles A u - H g 18 photochemical reduction 7, 84 photoelectron spectroscopy 44 platinum particles 10, 36 polycarboxylic acids 17, 84 poly-p-xylylene films 57 polypyrrole nanowires 13, 192 porous structure 13, 15 probe microscopy 39-41 quantum dots, biolabels 205 radiation reduction 7, 17-18 rare-earth elements, reactions 69-74 reaction kinetics 12 reactions in micelles and emulsions 12, 49 of magnesium particles 4 7 - 5 6 rhodium particles 12, 176 ruthenium particles 10 samarium complexes 74, 79, 83 reactions 70, 72, 78, 80 spectra 76 self-organization 157, 196, 198, 205, 207 semiconductors 188-196

sensors N 0 2 195 S 0 2 192 temperature 193 shape-control 12 silica, mesoporous 16 silicon particles 147 silver clusters 10, 66-67, 84-86, 91, 165 silver particles 9, 166, 179, 188 simulation A g n P b m clusters 91 heteroclusters 91-93 systems 9 2 - 9 3 , 95 size effects definition 5, 157 external 4 internal 4 optical spectra 162-167 sodium particles 6 sol-gel synthesis 19 solvated metal particles 125 sonochemical method 19

stabilization by mesogenes 65-68 by polymers 57-64 by solvent 125 supercritical solutions 20 tetrapod particles 136 theoretical simulation 87, 98, 132 thermodynamic consequences influence of p H 175, 178, 188, 192 melting point 204 shift chemical equilibrium 170 titanium, reactions 112 tungsten particles 118 vanadium particles 120 X - r a y fluorescence spectroscopy 43 zeolite 15 zinc-nanooxide, reactions 186 zinc-selenium particles 189