Provides a systematic and coherent picture of the solution-based methods for the preparation of noble metal-based composite nanomaterials, their characterization, and potential applications in electrocatalysis Within the last decade, the development of wet-chemistry methods has led to the blossom of research in composite nanomaterials. However, the design and synthesis of composite nanomaterials with controlled properties remains a significant challenge. This book summarizes the solution-based methods for the preparation of noble metal-based composite nanomaterials. It examines their characterization, as well as their use in electrocatalysis. It also discusses the intrinsic relationship between the catalytic properties and the physical /chemical effects in the composite materials, and offers some perspectives for the future development of metal-based composite nanomaterials. In addition, the book not only provides a systematic and coherent picture of this field, but also inspires rethinking of the current processing technologies. Noble Metal-Based Nanocomposites: Preparation and Applications offers in-depth chapter coverage of ethanol-mediated phase transfer of metal ions and nanoparticles. It presents the full range of nanocomposites consisting of chalcogenide semiconductors and gold, silver sulfide, or other noble metals. It also examines core-shell structured cadmium selenide-platinum nanocomposites; Pt-containing Ag2S-noble metal nanocomposites for direct methanol fuel cells operated at high fuel concentrations; and nanocomposites consisting of metal oxides and noble metals. In addition, the book looks at scientific issues derived from noble metal-based nanocomposites. -Covers all of the preparations of noble metal-based nanocomposites and their numerous applications -Highlights some of the recent breakthroughs in the design, engineering, and applications of noble metal-based nanocomposites -Appeals to a wide range audience, especially researchers in the areas of catalysis, chemistry, chemical engineering, materials synthesis and characterization, and fuel cell Noble Metal-Based Nanocomposites: Preparation and Applications is an excellent book for inorganic chemists, materials scientists, catalytic chemists, chemical engineers, and those interested in the subject.
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 BrustSchiffrin 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 Advancesin 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 PbTeAu 91
3.3.4.2 Cu2SAu 93
3.3.4.3 Bi2S3Au 94
3.3.4.4 SnSAu 94
3.3.4.5 ZnSeAu 96
3.3.4.6 Cu2ZnSnS4Au (CZTSAu) 97
3.3.4.7 Mapping of Photogenerated Electron and Hole Separation in Single SemiconductorMetal Nanocomposites 100
3.4 Growth of Chalcogenide Semiconductors on Gold Nanoparticles 102
3.5 Semiconducting Metal SulfideGold Nanocomposites upon Ethanol-Mediated Phase Transfer 110
3.5.1 Ag2SAu 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 Ag2SAu Nanocomposites 116
3.5.2 HgSAu 119
3.5.3 Semiconducting Metal SulfideGold Nanocomposites 121
3.5.3.1 CdSAu 122
3.5.3.2 Metal SulfideAu 125
3.5.3.3 PbSAg/Au Nanocomposites 127
3.6 SemiconductorGold Nanocomposites by a Two-phase Strategy 132
3.7 Special Gold-Related Nanocomposites 132
3.8 SemiconductorGold 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 SemiconductorSilver Nanocomposites 150
4.3 SemiconductorPlatinum Nanocomposites 158
4.4 Nanocomposites Consisting of Semiconductors and Other Noble Metals 171
4.5 SemiconductorDual 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 Ag2SNoble Metal Nanocomposites 196
5.4 Multiple Ag2SNoble Metal Nanocomposites 200
5.5 Electrocatalytic Property of Pt-Containing Ag2SNoble Metal Nanocomposites for Methanol Oxidation Reaction and Oxygen Reduction Reaction 203
5.6 Electrocatalytic Property of Pt-Containing Ag2SNoble Metal Nanocomposites for Formic Acid Oxidation Reaction 209
5.7 Summary 211
References 212
6 Nanocomposites Consisting of Chalcogenide Semiconductors and Noble Metals by StructuralTransformations 217
6.1 Introduction 217
6.2 Inside-Out Diffusion of Ag in CoreShell 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 AuPt 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 CoreShell 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 CoreShell-Structured Cadmium SelenidePlatinum 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 CdSePt Nanocomposites with CoreShell Constructions 258
7.3.1 Characterizations of CdSe Nanocrystals and CoreShell-Structured CdSePt Nanocomposites 259
7.3.2 The Compressive Strain Effect of CdSe Core on the Pt Shell 262
7.3.3 Electrochemical Activity of CoreShell-Structured CdSePt Nanocomposites for Oxygen Reduction and Methanol Oxidation Reactions 264
7.4 Further Efforts in CoreShell-Structured SemiconductorNoble Nanocomposites 269
7.5 Summary 271
References 272
8 Pt-Containing Ag2SNoble Metal Nanocomposites for Direct Methanol Fuel Cells Operated at High Fuel Concentrations 277
8.1 Introduction 277
8.2 Ternary Au@Ag2SPt Nanocomposites as Selective Electrocatalysts at DMFC Anode 278
8.3 CoreShellShell Au@Ag2S@Pt Nanocomposites as Selective Electrocatalysts at DMFC Anode 281
8.4 Cage-Bell-Structured PtRu Nanoparticles as Selective Electrocatalysts at DMFC Cathode 283
8.5 CoreShell-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 OxideNoble Metal Nanocomposites 304
9.4 Dumbbell-Like Metal OxideNoble Metal Nanocomposites 311
9.5 High-Order Nanocomposites 327
9.6 RuO2Au Nanocomposites as Electrode Materials for Supercapacitors 335
9.6.1 RuO2/C Nanocomposites 336
9.6.2 RuO2Au/C Nanocomposites 336
9.6.3 Electrochemical Properties of RuO2/C and RuO2Au/C Nanocomposites 339
9.7 Hollow-Structured MOxRuO2 (M = Co, Cu, Fe, Ni, CuNi) Nanocomposites as Highly Efficient Electrodes for Supercapacitors 342
9.8 CuOPd Nanocomposites with Atomic Dispersion of Pd for Catalytic Removal of Benzene 358
9.8.1 Bimetallic CuPd Nanoalloys with Different Pd/Cu Molar Ratios 360
9.8.2 Calcination of Bimetallic CuPd Nanoalloys Supported on -Al2O3 Substrates 361
9.8.3 Reducibility of -Al2O3-Supported CuPd Nanoalloys after Calcination 365
9.8.4 Catalytic Activities of -Al2O3-Supported CuPd 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 DotAu Hybrids 395
10.3.4 Extraction of Au from Au-Containing Alloy Nanoparticles 397
10.4 Synthesis of PbSeAu Nanocomposites with Different Morphologies 401
10.4.1 Synthesis of PbSe Seeds 402
10.4.2 Synthesis of PbSeAu Nanocomposites 403
10.4.3 Mechanism for the Nucleation and Growth of Au on PbSe Nanocrystals 406
10.5 Fine Ag2SPt 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
