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Contents

Foreword

vii
ix

Introduction

Survey of the Problem and Certain Definitions

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

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8
12
16
20
30
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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

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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

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51
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75
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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

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89
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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

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103
112
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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

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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

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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

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184
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202

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Conclusion

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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