Metal nanoparticles and nanoalloys / edited by Roy L. Johnston, J.P. Wilcoxon.

Format:

Book

Contributor:

Johnston, R. L. (Roy Luigi)

Wilcoxon, J. P. (Jess P.)

Series:

Frontiers of nanoscience ; 3.

Frontiers of nanoscience / series editor, Richard E. Palmer, 1876-2778 ; vol. 3

Language:

English

Subjects (All):

Nanoparticles.

Nanostructured materials.

Physical Description:

ix, 302 pages : illustrations ; 24 cm.

Place of Publication:

Amsterdam ; Boston : Elsevier, [2012]

Summary:

The field of nanoscience has undergone tremendous growth in the past decade as the, number of applications of nanoparticles and nanostructured materials have proliferated. Metal nanoparticles have attracted particular interest due to their potential for applications in areas as diverse as catalysis, medicine and optoelectronics. The chemical and physical properties of metal nanoparticles can vary smoothly or discontinuously with nanoparticle size, depending on the size regime and the property. In the case of bi- or multimetallic nanoparticles ("nanoalloys"), these properties also depend on the elemental composition and the chemical ordering - how the metals are distributed in the nanoparticles. It is this tunability of behaviour that makes metal nanoparticles and nanoalloys so versatile and appealing.

This book begins with a tutorial introducing the theoretical ideas and models which have been developed to understand metal nanoparticles. It gives an overview of experimental methods for generating and characterizing metal nanoparticles and nanoalloys and of their properties and applications, providing an introduction to material covered in more depth in subsequent chapters. A major theme of all the chapters is the effect of nanoparticle size, shape and surface chemistry on their properties - especially optical and catalytic properties.

Key features

A single source of information on nanoparticles with critical reviews of models and experiments

Provides direction for students and young researchers in nanoscience from leading experts in the field

Expert opinions on some of the most important developments and future directions in nanoparticles and nanotechnology. Book jacket.

Contents:

1 Metal Nanoparticles and Nanoalloys / Roy L. Johnston Johnston, Roy L. 1

1 Introduction 1

1.1 Nanoparticles 1

1.2 History of the Use and Study of Metal Nanoparticles 2

1.3 Nanoalloys 5

2 Synthesis of Metal Nanoparticles 8

2.1 Cluster Molecular Beams 8

2.2 Reduction of Metal Salts 9

2.3 Decomposition of Metal Complexes 9

2.4 Ion Implantation 9

3 Characterisation and Measurement Methods 9

3.1 Mass Spectrometry 10

3.2 Diffraction Techniques 10

3.3 Microscopy 10

3.4 X-ray Spectroscopy 12

3.5 Other Spectroscopic Techniques 13

3.6 Measurements of Magnetism and Polarizability 16

3.7 Ion Scattering 16

3.8 Electrochemistry 16

3.9 Ion Mobility Measurements 17

4 Theoretical Studies of Metal Nanoparticles 17

4.1 Theoretical Models of Bonding in Metal Nanoparticles 17

4.2 Computational Methods 21

4.3 Global Optimisation and Energy Landscape Exploration 23

4.4 Further Computational Studies 26

5 Properties and Applications 26

5.1 Structures 26

5.2 Optical Properties 29

5.3 Magnetic Properties 31

5.4 Biomedical Applications 31

5.5 Reactivity and Catalysis 32

5.6 Size-dependent Metal-Non-metal Transitions in MNPs 35

6 Summary 38

Acknowledgements 38

References 38

2 Nanoparticles-Preparation, Characterization and Physical Properties / J. P. Wilcoxon Wilcoxon, J. P. 43

1 Introduction 43

2 Nanoparticle Synthetic Methods 48

2.1 Inverse Micelle Synthesis Method 48

2.2 Particle Formation by Chemical Reduction in the Presence of Stabilizers 50

2.3 Organometallic Decomposition in the Presence of Stabilizers 52

3 Nanoparticle Characterization 53

3.1 Synthesis Optimization Through Characterization Feedback 53

3.2 Transmission Electron Microscopy (TEM, HRTEM) 54

3.3 High-Pressure Liquid Chromatography and Size Exclusion Chromatography 55

3.4 Online Absorbance Spectroscopy 61

3.5 Nanoparticle Atomic Composition and Structural Characterization 62

4 SEC Analysis of Inverse Micelle Synthesis 64

4.1 Au Nanoparticles 64

4.2 Ag Nanoparticles 67

5 Optical Properties of Ag/Au, Au/Ag core/shell and Nanoalloys 70

5.1 Heterogeneous Growth of Homo- and Heteroatomic Metal Particles 70

5.2 Heterogeneous Growth of Homoatomic Particles (Au Atoms on Au Nanocrystal Seeds) 71

5.3 Heterogeneous Deposition of Ag on Au and Au on Ag 73

5.4 Nanoalloys of Au and Ag and the Effect of Alloying on Ligand Binding 76

5.5 Metal Nanoparticle Luminescence and the Role of Surfactants as Etchants 80

5.6 Effects of Etching and Ageing on Nanoparticles 86

5.7 Ageing Effects on Particle Size Distributions 92

6 Magnetic Behaviour of Base Metal Nanoparticles 96

6.1 Effect of Alloying with Magnetic and Non-Magnetic Metals 102

7 Nanoparticle Catalytic Properties and Applications 106

7.1 Nanoparticle Catalysts in Coal Technology 109

7.2 Nanoparticles and the Future of Small Molecule "Fixation" Redox Reactions 117

7.3 Nanoparticle Photocatalysis 118

8 Summary 121

Acknowledgements 123

References 123

3 Ligand-Protected Gold Nanoclusters as Superatoms-Insights from Theory and Computations / Hannu Häkkinen Häkkinen, Hannu 129

1 Introduction and Scope 129

2 Synthesis of Ligand-Protected Gold Nanoparticles 130

3 The Noble Metal-Thiolate Bond 132

4 Ligand-Protected Gold Cluster Superatoms 135

4.1 Early Models 135

4.2 The Divide and Protect Concept 136

4.3 The Experimental Breakthroughs: X-Ray Crystallography for All-Thiolate Protected Au₁₀₂ and Au₂₅ Clusters and the Success of the Superatom Model 137

4.4 Phosphine-Stabilized Au₁₁ and Au₃₉ Clusters: Superatoms with 8 and 34 Electrons 142

4.5 The Unifying Superatom Concept 144

4.6 The Story of Au₃₈: A Deformed Superatom with 14 Metallic Electrons in a Nanorod-Shaped Core with a Chiral Gold-Thiolate Surface Layer 144

4.7 Use of the Superatom Concept to Understand Reactivity: The Electronic Structure of the Gold Nanocluster Core, Dioxygen Activation and CO Oxidation 146

5 Outlook and Challenges for Theory 149

5.1 Yet Unkown Cluster Compositions and Structures 151

5.2 Ligand-Exchange Reactions 152

5.3 Ligand-Protected Clusters as Nanocatalysts 153

Acknowledgements 154

References 154

4 Theoretical Modelling of Oxide-Supported Metal Nanoclusters and Nanoalloys / Alessandro Fortunelli Fortunelli, Alessandro, Riccardo Ferrando Ferrando, Riccardo 159

1 Introduction 159

2 Methods 160

2.1 Density-Functional Methods 160

2.2 Empirical Potentials 162

2.3 Effective Hamiltonians and Continuum Methods 166

3 Structural Concepts 167

3.1. Magic Clusters 168

4 Algorithms for Global Optimisation 169

4.1 Small Clusters 170

4.2 Aggregates with 20≤N≤150 171

4.3 Aggregates with 150≤N≤1000 172

4.4 Larger Aggregates 172

4.5 The Investigated Metal and Oxide Systems 173

5 Small Clusters 174

6 Aggregates with 20≤N≤150 185

7 Aggregates with N≥150 198

8 Exotic Substrates 200

9 Conclusions 204

Acknowledgements 204

References 205

5 Scanning Transmission Electron Microscopy Studies of Mono- and Bimetallic Nanoclusters / Ziyou Li Li, Ziyou 213

1 Introduction 213

2 Scanning Transmission Electron Microscopy 214

2.1 The Scanning Transmission Electron Microscopy 214

2.2 Physics of Image Formation in STEM 218

2.3 Quantitative Analysis of STEM Images 220

3 Nanocluster Characterization 223

3.1 Case Study I: Monometallic Nanoclusters 223

3.2 Case Study II: Bimetallic Nanoclusters 236

4 Concluding Remarks 244

References 245

6 Application of Gold Nanoparticles in Catalysis / Graham J. Hutchings Hutchings, Graham J., Jennifer K. Edwards Edwards, Jennifer K. 249

1 Introduction 249

2 Reactions Involving Carbon Monoxide 250

2.1 Carbon Monoxide Oxidation 250

2.2 Water Gas Shift Reaction 263

2.3 Applications of Low Temperature CO Oxidation 266

3 Selective Oxidation 268

3.1 Epoxidation 270

3.2 Oxidation of Alcohols and Aldehydes 273

3.3 C-H Bond Activation 277

4 Reactions Involving Hydrogen 278

4.1 Hydrogenation of α,β-Unsaturated Aldehydes 278

4.2 Direct Hydrogen Peroxide Synthesis 282

5 Summary 286

References 287.

Notes:

Includes bibliographical references and index.

ISBN:

9780080963570

0080963579

OCLC:

761856717