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NanoscaleMaterialsinChemistry.EditedbyKennethJ.Klabunde Copyright#2001JohnWiley&Sons,Inc. ISBNs:0-471-38395-3(Hardback);0-471-22062-0(Electronic) NANOSCALE MATERIALS IN CHEMISTRY NANOSCALE MATERIALS IN CHEMISTRY Edited by Kenneth J. Klabunde A John Wiley & Sons, Inc., Publication NewYork (cid:1) Chichester (cid:1) Weinheim (cid:1) Brisbane (cid:1) Singapore (cid:1) Toronto Designationsusedbycompaniestodistinguishtheirproductsareoftenclaimedastrademarks.Inall instanceswhereJohnWiley&Sons,Inc.,isawareofaclaim,theproductnamesappearininitialcapitalor ALLCAPITALLETTERS.Readers,however,shouldcontacttheappropriatecompaniesformorecomplete informationregardingtrademarksandregistration. Copyright#2001byJohnWiley&Sons,Inc.Allrightsreserved. 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To Linda CONTENTS Preface ix Contributors xi 1 Introduction to the Nanoworld 1 KennethJ.Klabunde 2 Metals 15 GunterSchmid 3 Semiconductor Nanocrystals 61 M.P. Pileni 4 Ceramics 85 AbbasKhaleelandRyan M.Richards 5 Metal Nanoparticles: Double Layers, Optical Properties, and Electrochemistry 121 PaulMulvaney 6 Magnetism 169 C.M. Sorensen 7 Chemical and Catalytic Aspects of Nanocrystals 223 KennethJ.KlabundeandRavichandraS. Mulukutla 8 Specific Heats and Melting Points of Nanocrystalline Materials 263 OlgaKoperandSlawomir Winecki 9 Applications of Nanocrystals 279 JohnParker Index 287 vii PREFACE Nanotechnologyisalmostahouseholdwordnow-a-days,oratleastsomewordwith ‘‘nano’’ in it, such as nanoscale, nanoparticle, nanophase, nanocrystal, or nano- machine.ThisfieldnowenjoysworldwideattentionandaNationalNanotechnology Initiative (NNI) is about to be launched. This field owes its parentage to investigations of reactive species (free atoms, clusters, reactive particles) throughout the 1970s and 1980s, coupled with new techniquesandinstruments(pulsedclusterbeams,innovationsinmassspectrometry, vacuum technology, microscopes, and more). Excitement is high and spread throughout different fields, including chemistry, physics, material science, engineering, and biology. This excitement is warranted becausenanoscalematerialsrepresentanewrealmofmatter,andthepossibilitiesfor interesting basic science as well as useful technologies for society are widespread and real. Inspiteofallthisinterest,thereisaneedforabookthatservesthebasicscience community, especially chemists. This book was written to serve first as a advanced textbook for advanced undergraduate or graduate courses in ‘‘nanochemistry’’, and second as a resource and reference for chemists and other scientists working in the field. Therefore, the readerwillfindthatthechaptersarewrittenasateachermightteachthesubject,and notsimplyasareferencework.Therefore,wehopethatthisbookwillbeadoptedfor teaching numerous advanced courses in nanotechnology, materials chemistry, and related subjects. The coverage of this volume is as follows: First, a detailed introduction of nanotechnologyandabriefhistoricalaccountisgiven.Thisisfollowedbymasterful chaptersonnanosizemetalsbyGunterSchmid,semiconductorsbyMariePileni,and ceramics by Abbas Khaleel and Ryan Richards. The next chapters deal more with properties, such as optical properties by Paul Mulvaney, magnetic properties by ChrisSorensen,catalyticandchemicalpropertiesbytheeditorandRaviMulukutla, physicalpropertiesbyOlgaKoperandSlawomirWinecki,andfinallyashortchapter on applications of nanomaterials by John Parker. The editor gratefully acknowledges the contributing authors of these chapters, who are world renowned experts in this burgeoning field of nanotechnology. Their enthusiasmandhardworkareverymuchappreciated.Theeditoralsoacknowledges the help of his students and colleagues, as well as his family for their patience and understanding. Kenneth J. Klabunde ix CONTRIBUTORS DR. ABBAS KHALEEL, Dept. of Chemistry, UAE University, Al-Ain, United Arab Emirates PROFESSORKENNETHJ.KLABUNDE, Dept.ofChemistry,KansasState University, Manhattan, KS 66506 DR. OLGA KOPER, Nanoscale Materials, Inc., 1500 Hayes Drive, Manhattan, KS 66502 DR. RAVICHANDRA S. MULUKUTLA, Department of Chemistry, Kansas State University, Manhattan, Kansas 66506 DR. PAUL MULVANEY, Advanced Mineral Products, School of Chemistry, University of Melbourne, Parkville, VIC 3052, Australia DR. JOHN C. PARKER, 1588 Clemson Dr., Naperville, IL 60565 PROFESSOR MARIE PILENI, Department of Chemistry, Laboratorie SRSI, URA CNRS 1662, Universite P. et M. Curie (Paris VI), BP52, 4 Place Jussieu, 75231 Paris Cedex 05, France DR. RYAN RICHARDS, Dept. of Chemistry, Max Planck Institute, Kaiser Wilhelm Platz 1, 45470 Mulheim an der Ruhr, Germany PROFESSOR GUNTER SCHMID, Institute fur Anorganische Chemie, Universitat Essen, Essen, Germany PROFESSOR CHRIS SORENSEN, Dept. of Physics, Cardwell Hall, Kansas State University, Manhattan, KS 66506 DR. SLAWOMIRWINECKI, Nanoscale Materials, Inc., 1500 Hayes Drive, Manhat- tan, KS 66502 xi Index 1D Bacteria, 7 Assemblies, 52 Bactericide, 253 Channels, 53 Ballmilling, 239 Defined Steps, 53 Band Structure, 18 Nanoclusters, 52 Band Theory, 187 Pores, 53 Bandgap, 62, 64 2D Assemblies, 50 Bandgap Bowing, 70 3D Microcrystals, 50 Barkhausen Effect, 199, 200 Acid Gases, 247 Batteries, 5, 240 Acid-Base, 111 Beryllium, 17 Active Metals, 244, 246 BET, 9 Adsorbate Damping, 164 Bethe-Slater Curve, 187, 216 Adsorbents, 223, 238 Bioassays, 165 Adsorption, 112, 239 Biological Warfare, 253 Aerogel, 98 Biomedical, 283 Aerosol Methods, 88 Bismuth-Manganese, 187 Aerosol Thermolysis, 92 Bloch’s Law, 216 AFM, 8 Constant, 184, 216, 218 Alkane Isomerization, 237 Exponent, 184, 216 Alkylation, 234 Block Copolymers, 255 Alloy Semiconductors, 69 Blocking Temperature, 207, Alloys, 189 208 Aluminosilicates, 241 Bonding in Ceramics, 104 Aluminum Nitride, 101 Borohydride, 240 Aluminum Oxide, 85, 95, 98, 101, Brillouin Functions, 181, 184 104, 114 Cadmium Sulfide Melting, 274 Anatase, 110 Cadmium, 246 Anisotropy, 194 Selenide, 63, 66 Crystal, 193 Sulfide, 63, 66 Magnetocrystalline, 193 Telluride, 63, 64 Shape, 195, 203 Calcium Fluoride, 86 Surface, 216 Calcium Oxide, 85 Antiferromagnetic, 186, 190, 191 Capacitance, 32 AOT, 62 Nanoparticles, 153 Applications, 279 Carbon Dioxide, 247 Arrangement Nanoparticles, 46 Carbon Nanotubes, 243 Asymmetric Catalysis, 230 Catalysis, 37, 223 Atomic Vibrations, 273 Ceramics, 2, 85 287 288 INDEX Cerium Oxide, 236 Destructive Adsorbents, 3 Chain-melting, 80 Destructive Adsorption 248, 250, Chemical Reagents, 244 251 Chemical Vapor Condensation, 92 Diblock Copolymers, 50 Chemical Warfare, 252 Dielectric Function, 146 Chloride Process, 94 Dielectric Response, 145 Chlorination, 235 Differential Scanning Calorimetry, 9 Chromium Oxide, 85 Diffuse Layer, 127, 129 Cluster Grignard, 245 Microparticles, 128 Clusters, 11 Nanoparticles, 129 Cobalt Clusters, 213 Diffusion Bonding, 114 Cobalt-Copper, 215 Diffusion Flame, 94 Coercivity, 198, 201, 209 Dilute Magnetic Semiconductor, 63, Coherent Rotation, 205 70 Colloid, 11 DNA, 2 Colloidal Crystals, 48 Drude Model, 148 Color, 19, 28, 36 Drugs, 1 Colorants, 281 DSC, 9 Conductivity, 17, 31 Dulong-Petit Law, 264 Copper Oxide, 234 Dyes, 2, 255 Copper-Nickel, 215 Effective Reaction Radius, 135 Core-Shell, 156, 157, 215, 217 Einstein Model, 266 Gold-Silicon Dioxide, 158, 159 Electrical double layer, 124 Gold-Silver, 156 Electrode-Colloid, 160, 161 Lead-Silver, 157 Capacitance, 164 Magnesium Fluoride-Iron, Plasmon Band, 163 217 Potential, 163 Magnesium-Iron, 215, 217 Electrodes, 4 Corrosion Resistant, 281 Electroluminescent, 284 Coulomb Blockade, 32 Electron Density, 216 Curie, 179, 181 Electron Mobility, 31 Constant, 179, 181 Electron Transfer Law, 182 Activation Controlled, 137 Plot, 182 Electronegativity, 216 Temperature, 192 Electronic Effects, 226 Curie-Weiss Law, 71, 182 Electronics, 4, 283 Curling, 204 Encapsulated Iron, 211 Dead Layer, 216 Energy Dissipation, 165 Debye, 121, 122 Environmental Remediation, 3 Debye Model, 266 ESR, 108 Debye Theory, 265 Ethylene Alkylation, 234 Defects, 105 Fanning, 204 Dehydrohalogenation, 238 Fermi Level, 17 Densify, 113 Ferrimagnet, 191, 192 Density of States, 17, 188 Ferrofluids, 5, 233, 255 INDEX 289 Ferromagnetic, 172, 173, 174, 177, Laser Desorption-MS, 9 183, 184, 191 Laser Methods, 91 Field Cooled, 208 LD-FTICR-MS, 9 Flame Reactors, 88, 92 Lead, 246 Flash Photolysis, 134 Lead Zirconate, 110 Flat Flame Reactor, 94 Lead Zironate Titanate, 110 Flow Gas Evaporation, 89 Lewis Acids, 236 Fluids, 255 Ligation Effects, 214 Free Electron Model, 17 Light Absorption Fullerenes, 243 Colloids, 143 Gas Condensation, 88 Lithium Clusters, 16 Glasses, 121 Magnesium, 239 Gold, 121, 231 Magnesium Clusters, 245 Gold Cluster, 35 Magnesium Fluoride, 186 Gold Melting, 274 Magnesium Oxide, 85, 105, 107 Gold Standard, 239 Magnetic Anisotropy, 193 Grignard Reagents, 244, 246 Magnetic Domains, 195 Hamaker Constant, 131, 132 Magnetic Fluids, 5 Hardness, 113, 280 Magnetic Semiconductor, 63 Heat of Fusion, 273 Magnetics, 283 Helmholtz Layer, 124, 137 Magnetism, 25, 169 High Resolution TEM, 8 Origins, 169 HRTEM, 8 Permeability, 171 Hydrogen Adsorption, 239 Susceptibility, 171 Hydrogen Formation, 138 Units, 170, 171 Hydrogen Sulfide, 250 Variables, 170 Hysteresis, 192, 198, 202, 203 Magnetization Remanence, 198 Indium-Aluminum, 275 Mass Transfer Limited, 134 Indium-Iron, 275 MCM-41, 242 Information Storage, 2 Mechanical Materials, 280 Inks, 2, 255 Mechanochemical, 88 Inner Core, 21 Mechanochemical Synthesis, 104 Insulators, 2, 85 Melting Points, 23, 270, 271 Interdigitation, 80 Metal Bonding, 15 Interfacial Effects, 212, 215 Metal Carbides, 88 Inverse Micelles, 165 Metal Hydrides, 240 Ion Exchange, 249 Metal Organics, 92 Iridium, 233 Metal Oxides, 247 Iron Clusters, 213 Metallic, 19 Iron Crystallites, 186 Methanol Synthesis, 234 Iron Oxide, 85 Microemulsion, 62 Iron-Magnesium Fluoride, 215, 217 Mie Resonance, 29, 147 Iron-Mercury, 215 Mie Theory, 121 Isotope Exchange, 251 Molecular Orbitals, 20 Langevin Model, 178 Molybdenum Carbide, 101