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About the Author xi Preface xiii Acknowledgments xv List of Abbreviations xvii 1 An Introduction to Noble Metal-Based Composite Nanomaterials 1 1.1 Materials at Nanometer Scales 1 1.2 Emergence of Composite Nanomaterials 3 1.3 General Concepts in Wet Chemistry Synthesis of Composite Nanomaterials 6 1.4 Characterizations of Composite Nanomaterials 11 1.5 The Scope of This Book 14 1.6 The Road Ahead 18 References 19 2 Ethanol-Mediated Phase Transfer of Metal Ions and Nanoparticles 35 2.1 Introduction 35 2.2 Early Studies in Phase Transfer of Noble Metal Nanoparticles 36 2.3 Brust-Schiffrin Method 38 2.4 Phase Transfer Through Ligand Exchange 41 2.5 Phase Transfer Through Electrostatic Interaction 45 2.6 Phase Transfer of Nanoparticles from Organic to Aqueous Phase 47 2.7 Ethanol-Mediated Phase Transfer 48 2.7.1 Ethanol-Mediated Phase Transfer of Metal Ions 48 2.7.2 Ethanol-Mediated Phase Transfer of Metal Nanoparticles 53 2.8 Recent Advances in Phase Transfer 57 2.9 Summary 60 References 60 3 Nanocomposites Consisting of Chalcogenide Semiconductors and Gold 69 3.1 Introduction 69 3.2 Phosphine-Free Synthesis of Metal Selenide Nanocrystals 70 3.3 Deposition of Au on Chalcogenide Semiconductor Nanocrystals 72 3.3.1 Contributions from the Banin Group 72 3.3.2 Contributions from the Other Research Groups 81 3.3.3 Nanocomposites Consisting of Chalcogenide Semiconductors and Gold by Self-assembly 88 3.3.4 Case Studies Associated with Nanocomposites Consisting of Chalcogenide Semiconductors and Gold 91 3.3.4.1 PbTe-Au 91 3.3.4.2 Cu2S-Au 93 3.3.4.3 Bi2S3-Au 94 3.3.4.4 SnS-Au 94 3.3.4.5 ZnSe-Au 96 3.3.4.6 Cu2ZnSnS4-Au (CZTS-Au) 97 3.3.4.7 Mapping of Photogenerated Electron and Hole Separation in Single Semiconductor-Metal Nanocomposites 100 3.4 Growth of Chalcogenide Semiconductors on Gold Nanoparticles 102 3.5 Semiconducting Metal Sulfide-Gold Nanocomposites upon Ethanol-Mediated Phase Transfer 110 3.5.1 Ag2S-Au 111 3.5.1.1 Formation of Monodisperse Ag2S Nanocrystals in Toluene at Room Temperature 111 3.5.1.2 Structural Evolutions of Ag2S Nanocrystals 112 3.5.1.3 Growth Mechanism of Ag2S Nanocrystals 113 3.5.1.4 Influence of Temperature and Ag/S Molar Ratios on the Growth of Ag2S Nanocrystals 115 3.5.1.5 Synthesis of Dimeric Ag2S-Au Nanocomposites 116 3.5.2 HgS-Au 119 3.5.3 Semiconducting Metal Sulfide-Gold Nanocomposites 121 3.5.3.1 CdS-Au 122 3.5.3.2 Metal Sulfide-Au 125 3.5.3.3 PbS-Ag/Au Nanocomposites 127 3.6 Semiconductor-Gold Nanocomposites by a Two-phase Strategy 132 3.7 Special Gold-Related Nanocomposites 132 3.8 Semiconductor-Gold Nanocomposites for Efficient Three-component Coupling of Aldehyde, Amine, and Alkyne in Water 135 3.9 Summary 137 References 138 4 Nanocomposites Consisting of Chalcogenide Semiconductors and Other Noble Metals 149 4.1 Introduction 149 4.2 Semiconductor-Silver Nanocomposites 150 4.3 Semiconductor-Platinum Nanocomposites 158 4.4 Nanocomposites Consisting of Semiconductors and Other Noble Metals 171 4.5 Semiconductor-Dual Metal Nanocomposites 176 4.6 Summary 186 References 186 5 Nanocomposites Consisting of Silver Sulfide and Noble Metals 193 5.1 Introduction 193 5.2 Aqueous Synthesis of Ag2S Nanocrystals 194 5.3 Binary Ag2S-Noble Metal Nanocomposites 196 5.4 Multiple Ag2S-Noble Metal Nanocomposites 200 5.5 Electrocatalytic Property of Pt-Containing Ag2S-Noble Metal Nanocomposites for Methanol Oxidation Reaction and Oxygen Reduction Reaction 203 5.6 Electrocatalytic Property of Pt-Containing Ag2S-Noble Metal Nanocomposites for Formic Acid Oxidation Reaction 209 5.7 Summary 211 References 212 6 Nanocomposites Consisting of Chalcogenide Semiconductors and Noble Metals by Structural Transformations 217 6.1 Introduction 217 6.2 Inside-Out Diffusion of Ag in Core-Shell Nanoparticles with Ag Residing in the Core or Internal Shell Regions 218 6.3 Nanocomposites Consisting of Ag2S and Hollow Noble Metal Nanoparticles 222 6.4 Nanocomposites Consisting of Ag2S and Bimetallic Au-Pt Cage-Bell Structures 226 6.5 Ternary Nanocomposites Consisting of Ag2S, Au, and Hollow Pt Nanoparticles 227 6.6 Electrochemical Properties of the Binary and Ternary Nanocomposites and Their Core-Shell Precursors 229 6.7 Nanocomposites Consisting of Ag2S and Palladium Nanoparticles and Their Electrochemical Properties 232 6.8 Nanocomposites Consisting of Ag2Se and Hollow Platinum Nanoparticles 235 6.9 Nanocomposites Consisting of CuS and Platinum Nanoparticles 238 6.10 Strategies for Further Enhancing the Catalytic Performance of Pt-Containing Noble Metal-Based Nanocomposites in Electrochemical Reactions 240 6.11 Summary 242 References 242 7 Core-Shell-Structured Cadmium Selenide-Platinum Nanocomposites 249 7.1 Introduction 249 7.2 Reversible Phase Transfer of Semiconductor and Noble Metal Nanoparticles 250 7.2.1 Ligand Exchange-Based Phase Transfer of Semiconductor and Noble Metal Nanoparticles from Organic Medium to Aqueous Phase 251 7.2.2 Electrostatic Interaction-Based Reversible Phase Transfer of Semiconductor and Noble Metal Nanoparticles between Organic Medium and Aqueous Phase 257 7.3 CdSe-Pt Nanocomposites with Core-Shell Constructions 258 7.3.1 Characterizations of CdSe Nanocrystals and Core-Shell-Structured CdSe-Pt Nanocomposites 259 7.3.2 The Compressive Strain Effect of CdSe Core on the Pt Shell 262 7.3.3 Electrochemical Activity of Core-Shell-Structured CdSe-Pt Nanocomposites for Oxygen Reduction and Methanol Oxidation Reactions 264 7.4 Further Efforts in Core-Shell-Structured Semiconductor-Noble Nanocomposites 269 7.5 Summary 271 References 272 8 Pt-Containing Ag2S-Noble Metal Nanocomposites for Direct Methanol Fuel Cells Operated at High Fuel Concentrations 277 8.1 Introduction 277 8.2 Ternary Au@Ag2S-Pt Nanocomposites as Selective Electrocatalysts at DMFC Anode 278 8.3 Core-Shell-Shell Au@Ag2S@Pt Nanocomposites as Selective Electrocatalysts at DMFC Anode 281 8.4 Cage-Bell-Structured Pt-Ru Nanoparticles as Selective Electrocatalysts at DMFC Cathode 283 8.5 Core-Shell-Structured Au@Pd Nanoparticles with Thin Pd Shells as Selective Electrocatalysts at DMFC Cathode 286 8.6 A Prototype of the Membraneless Direct Methanol Fuel Cell 289 8.7 A Selective Electrocatalyst-Based Direct Methanol Fuel Cell (DMFC) Operated at High Concentration of Methanol 289 8.8 Summary 295 References 295 9 Nanocomposites Consisting of Metal Oxides and Noble Metals 301 9.1 Introduction 301 9.2 Gold-Based Nanocomposites for CO Oxidation at Low Temperature 302 9.3 Early Studies in Metal Oxide-Noble Metal Nanocomposites 304 9.4 Dumbbell-Like Metal Oxide-Noble Metal Nanocomposites 311 9.5 High-Order Nanocomposites 327 9.6 RuO2-Au Nanocomposites as Electrode Materials for Supercapacitors 335 9.6.1 RuO2/C Nanocomposites 336 9.6.2 RuO2-Au/C Nanocomposites 336 9.6.3 Electrochemical Properties of RuO2/C and RuO2-Au/C Nanocomposites 339 9.7 Hollow-Structured MOx-RuO2 (M = Co, Cu, Fe, Ni, CuNi) Nanocomposites as Highly Efficient Electrodes for Supercapacitors 342 9.8 CuO-Pd Nanocomposites with Atomic Dispersion of Pd for Catalytic Removal of Benzene 358 9.8.1 Bimetallic Cu-Pd Nanoalloys with Different Pd/Cu Molar Ratios 360 9.8.2 Calcination of Bimetallic Cu-Pd Nanoalloys Supported on -Al2O3 Substrates 361 9.8.3 Reducibility of -Al2O3-Supported Cu-Pd Nanoalloys after Calcination 365 9.8.4 Catalytic Activities of -Al2O3-Supported Cu-Pd Nanoalloys after Calcination for Benzene Oxidation 366 9.9 Strategies for Determining the Influence of Noble Metals on the Catalytic Performance of Nanocomposites 368 9.10 Summary 371 References 372 10 Scientific Issues Derived from Noble Metal-Based Nanocomposites 383 10.1 Introduction 383 10.2 Diffusion of Gold from the Inner Core to the Surface of Ag2S Nanocrystals 384 10.3 Coalescence of Au and Ag2S Nanocrystals at Room Temperature 391 10.3.1 Observation of Coalescence of Au and Ag2S Nanocrystals 391 10.3.2 Mechanism Responsible for the Coalescence of Au and Ag2S Nanocrystals 393 10.3.3 Removal of Au from Quantum Dot-Au Hybrids 395 10.3.4 Extraction of Au from Au-Containing Alloy Nanoparticles 397 10.4 Synthesis of PbSe-Au Nanocomposites with Different Morphologies 401 10.4.1 Synthesis of PbSe Seeds 402 10.4.2 Synthesis of PbSe-Au Nanocomposites 403 10.4.3 Mechanism for the Nucleation and Growth of Au on PbSe Nanocrystals 406 10.5 Fine Ag2S-Pt Nanocomposites Supported on Carbon Substrates for Methanol Oxidation Reaction 408 10.6 Summary 413 References 414 11 Conclusion and Perspectives 419 11.1 Creating a Favorable Solvent Environment for the Growth of Noble Metal-Based Nanocomposites 419 11.2 Synthesis of Composite Nanosystems and Understanding Their Underlying Chemistry 420 11.3 Exploring the Catalytic Properties of the Noble Metal-Based Nanocomposites for Energy Conversion and Storage 420 11.4 Investigating Other Scientific-Related Issues 421 References 421 Index 423

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