High-surface-area materials have recently attracted significant interest due to potential applications in various fields such as electrochemistry and catalysis, gas-phase catalysis, optics, sensors and actuators, energy harvesting and storage. In contrast to classical materials the properties of high-surface-area materials are no longer determined by their bulk, but by their nanoscale architecture. Nanoporous gold (np-Au) represents the fascinating class of mesoporous metals that have been intensively investigated in recent years. The current interest and the increasing number of scientific publications show that np-Au by itself is an outstanding nano-material that justifies a book devoted to all aspects of its properties and applications. The resulting publication is a discussion of this unique nano-material and is an accessible and comprehensive introduction to the field. The book provides a broad, multi-disciplinary platform to learn more about the properties of nanoporous gold from an inter-disciplinary perspective. It starts with an introduction and overview of state-of-the-art applications and techniques characterizing this material and its applications. It then covers the progress in research within the last years. The chapters are in-depth overviews written by the world's leading scientists in the particular field. Each chapter covers one technique or application so that the reader can easily target their favoured topic and will get the latest and state-of-the-art information in the field.

Introduction to Nanoporous Gold	p. 1
Nanoporous Gold	p. 1
Gold-Some Facts	p. 3
What Makes 'Nano' Special?	p. 5
Acknowledgments	p. 9
References	p. 9
Fundamental Physics and Chemistry of Nanoporosity Evolution During Dealloying	p. 11
Introduction	p. 11
Context-Pattern-Formating Instabilities and Nanostructure Fabrication	p. 11
Basic Phenomenology-Parting Limit and Critical Potential	p. 14
Short History of Theoretical Approaches for NPG Morphology Evolution	p. 16
Structural Considerations	p. 18
Percolation Basics	p. 18
Percolation Applied to Nanoporous Gold: The Parting Limit	p. 19
Thermodynamic Origins of the Critical Potential	p. 20
Kinetic of Porosity Evolution	p. 22
KMC Simulations	p. 22
Working Model for Porosity Evolution	p. 22
Rate-Limiting Behavior	p. 24
Analytical Models for Porosity Evolution	p. 25
Nanoporous Gold Throughout History	p. 26
Pre-Columbian Metallurgy	p. 26
Parting limits and Leonardo da Vinci	p. 27
Origins of Modern Dealloying Theory	p. 27
Summary	p. 27
Acknowledgement	p. 27
References	p. 28
Mechanistic Studies of Initial Dealloying	p. 30
Introduction	p. 30
Sample Preparation, Experimental Techniques, and Simulation	p. 31
Preparation of Cu₃Au (111) Surfaces	p. 31
Main Experimental Techniques	p. 33
Earlier Mechanistic Studies on Initial Dealloying	p. 35
Initial Dealloying of Cu₃Au (111)	p. 36
Clean Cu₃Au (111) Starting Surface	p. 37
Low and Medium Overpotential Regime	p. 37
Higher Overpotential Regime and Critical Potential	p. 42
Influence of Halide Additives	p. 43
Thiol-Modified Surfaces and Microstructuring	p. 44
Further Work and Perspectives	p. 48
Summary	p. 48
References	p. 48
Mechanical Properties of Nanoporous Gold	p. 51
Introduction	p. 51
Elastic-Plastic Deformation Behaviour	p. 52
Scaling Equations for Mechanical Properties	p. 52
Compression Tests	p. 53
Tensile Testing	p. 59
Fracture Behavior	p. 61
Modeling and Simulation Studies	p. 64
Summary	p. 65
Acknowledgments	p. 65
References	p. 66
Microfabrication of Nanoporous Gold	p. 69
Introduction	p. 69
Challenges in Fabrication of NPG Thin Films	p. 71
Dealloying by Free Corrosion	p. 73
Dealloying by Using Electrochemical Cells	p. 76
Potentiostatic Dealloying	p. 78
Galvanostatic Dealloying	p. 79
Fabrication of Micropatterned NPG Features	p. 86
Incorporation of Thin Film	p. 87
Fabrication of Microscale Structures	p. 88
Acknowledgments	p. 94
References	p. 94
Opticals Properties and Applications of Nanoporous Metals	p. 97
Introduction	p. 97
Theoretical Consideration: Opticals Properties of Metal Nanostructures	p. 99
Microstructure and Optical Properties of Nanoporous Metals	p. 102
Applications of Plasmonic Nanoporous Metals	p. 110
Biosensing with Plasmonic Nanosensors	p. 110
Surface-Enhanced Raman Scattering	p. 111
Nanoporous Plasmon-Enhanced Fluorescence	p. 126
Concluding Remarks	p. 129
References	p. 129
Actuation with High-Surface-Area Materials	p. 137
Introduction	p. 137
Actuation Driven by Capillary Forces	p. 138
General Phenomenology	p. 138
Description of Actuation in a Continuum Picture	p. 139
Surface-Stress-Induced Actuation: Experimental Characterization	p. 142
Structure	p. 143
Nanoporous Metals	p. 143
Carbon Nanomaterials	p. 145
Actuation	p. 148
Electrochemical Actuation with Nanoporous Metals	p. 148
Chemical Actuation with Nanoporous Metals	p. 153
Electrochemical Actuation with Carbon Nanotubes and Graphene	p. 154
Electrochemical Actuation with CA	p. 155
Two Important Characteristics	p. 159
Response Time	p. 159
Work Density	p. 159
References	p. 163
Surface Chemistry and Catalysis	p. 167
Introduction	p. 167
Surface Chemistry of Au	p. 170
Interaction of Au with Oxygen	p. 171
Interaction of Au with CO	p. 173
Alcohol Oxidation	p. 174
Gas-Phase Catalysis over Nanoporous Gold	p. 176
CO Oxidation	p. 176
Oxidation of Alcohols	p. 180
Liquid-Phase Catalysis	p. 184
Aerobic Oxidation of D-Glucose	p. 184
Oxidation of Silanes	p. 186
Surface Modification of Nanoporous Gold by Metal Oxides	p. 187
Gas-Phase Deposition: ALD-Modified Nanoporous Gold	p. 188
Liquid-Phase Deposition	p. 190
Summary and Remarks	p. 192
Acknowledgments	p. 193
References	p. 193
Electrocatalytical Properties of Nanoporous Gold	p. 199
Introduction	p. 199
Applications of NPG in Electrocatalysis	p. 200
Hydrogen Fuel Cells	p. 201
Electrochemical Oxidation of Methanol	p. 204
Electrochemical Oxidation of Formic Acid	p. 209
Electrochemical Oxidation of Glucose	p. 211
Applications of NPG in Electrochemical Sensors	p. 213
Non-enzymatic Sensors	p. 213
Enzyme-Based Sensors	p. 214
Immunosensors	p. 216
Environmental Monitoring	p. 217
Future Outlook	p. 220
Acknowledgments	p. 221
References	p. 221
Nanoporous Gold in Sensor Applications	p. 224
Introduction	p. 224
Enzyme-Immobilized NPG Electrochemical Biosensors	p. 225
Enzyme-Modified NPG Glucose Sensor	p. 226
Cytochrome C Encapsulated NPG Electrode for H₂O₂ Sensing	p. 226
Non-enzymatic NPG-Based Sensors for Physiologic Important Species	p. 227
Naked NPG Glucose Sensors	p. 227
Pt-Decorated NPG Glucose Sensors	p. 229
Gold-Decorated Nanoporous Copper Core-Shell Composite Glucose Sensors	p. 230
Pt-NPG Sensor for Escherichia coli (E. coli)	p. 231
NPG Sensor for Dopamine in the Presence of Ascorbic Acid	p. 233
NPG Immunosensor for Detection of Cancer Biomarker	p. 234
NPG-Based DNA Sensors	p. 235
NPG-Based DNA Sensors with [Ru(NH₃)₆]³⁺ Transducer	p. 235
NPG-Based DNA Sensor with PbS Nanoparticle Transducer Using Anodic Stripping Voltammetry	p. 238
NPG-Based DNA Sensor with Electrochemiluminescence of CdTe Quantum Dots	p. 238
NPG Sensors for Nitrogen-Containing Compounds	p. 242
NPG Sensor for Detection of p-Nitrophenol	p. 242
NPG Sensor for Amperometric Determination of Nitrite	p. 243
NPG as Promising Substrates for Surface-Enhanced Raman Scattering	p. 243
Concluding Remarks	p. 244
References	p. 245
Subject Index	p. 248
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Nanoporous Gold

9781849733748

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