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Developments in Electrochemistry

Science Inspired by Martin Fleischmann
1. Aufl.

von: Derek Pletcher, Zhong-Qun Tian, David Williams
85,99 €
Verlag:	Wiley
Format:	PDF
Veröffentl.:	03.06.2014
ISBN/EAN:	9781118694381
Sprache:	englisch
Anzahl Seiten:	392

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Beschreibungen

Titelbeschreibung

Martin Fleischmann was truly one of the ‘fathers’ of modern electrochemistry having made major contributions to diverse topics within electrochemical science and technology. These include the theory and practice of voltammetry and in situ spectroscopic techniques, instrumentation, electrochemical phase formation, corrosion, electrochemical engineering, electrosynthesis and cold fusion. While intended to honour the memory of Martin Fleischmann, Developments in Electrochemistry is neither a biography nor a history of his contributions. Rather, the book is a series of critical reviews of topics in electrochemical science associated with Martin Fleischmann but remaining important today. The authors are all scientists with outstanding international reputations who have made their own contribution to their topic; most have also worked with Martin Fleischmann and benefitted from his guidance. Each of the 19 chapters within this volume begin with an outline of Martin Fleischmann’s contribution to the topic, followed by examples of research, established applications and prospects for future developments. The book is of interest to both students and experienced workers in universities and industry who are active in developing electrochemical science.

Inhaltsverzeichnis

List of Contributors xiii 1 Martin Fleischmann – The Scientist and the Person 1 2 A Critical Review of the Methods Available for Quantitative Evaluation of Electrode Kinetics at Stationary Macrodisk Electrodes 21 Alan M. Bond, Elena A. Mashkina and Alexandr N. Simonov 2.1 DC Cyclic Voltammetry 23 2.1.1 Principles 23 2.1.2 Processing DC Cyclic Voltammetric Data 26 2.1.3 Semiintegration 29 2.2 AC Voltammetry 32 2.2.1 Advanced Methods of Theory–Experiment Comparison 35 2.3 Experimental Studies 36 2.3.1 Reduction of [Ru(NH3)6]3+ in an Aqueous Medium 36 2.3.2 Oxidation of FeII(C5H5)2 in an Aprotic Solvent 40 2.3.3 Reduction of [Fe(CN)6]3− in an Aqueous Electrolyte 42 2.4 Conclusions and Outlook 43 References 45 3 Electrocrystallization: Modeling and Its Application 49 Morteza Y. Abyaneh 3.1 Modeling Electrocrystallization Processes 53 3.2 Applications of Models 56 3.2.1 The Deposition of Lead Dioxide 58 3.2.2 The Electrocrystallization of Cobalt 60 3.3 Summary and Conclusions 61 References 63 4 Nucleation and Growth of New Phases on Electrode Surfaces 65 Benjamin R. Scharifker and Jorge Mostany 4.1 An Overview of Martin Fleischmann’s Contributions to Electrochemical Nucleation Studies 66 4.2 Electrochemical Nucleation with Diffusion-Controlled Growth 67 4.3 Mathematical Modeling of Nucleation and Growth Processes 68 4.4 The Nature of Active Sites 69 4.5 Induction Times and the Onset of Electrochemical Phase Formation Processes 71 4.6 Conclusion 72 References 72 5 Organic Electrosynthesis 77 Derek Pletcher 5.1 Indirect Electrolysis 79 5.2 Intermediates for Families of Reactions 80 5.3 Selective Fluorination 84 5.4 Two-Phase Electrolysis 85 5.5 Electrode Materials 87 5.6 Towards Pharmaceutical Products 88 5.7 Future Prospects 90 References 91 6 Electrochemical Engineering and Cell Design 95 Frank C. Walsh and Derek Pletcher 6.1 Principles of Electrochemical Reactor Design 96 6.1.1 Cell Potential 96 6.1.2 The Rate of Chemical Change 97 6.2 Decisions During the Process of Cell Design 98 6.2.1 Strategic Decisions 98 6.2.2 Divided and Undivided Cells 98 6.2.3 Monopolar and Bipolar Electrical Connections to Electrodes 99 6.2.4 Scaling the Cell Current 100 6.2.5 Porous 3D Electrode Structures 100 6.2.6 Interelectrode Gap 101 6.3 The Influence of Electrochemical Engineering on the Chlor-Alkali Industry 102 6.4 Parallel Plate Cells 105 6.5 Redox Flow Batteries 106 6.6 Rotating Cylinder Electrode Cells 107 6.7 Conclusions 108 References 109 7 Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS): Early History, Principles, Methods, and Experiments 113 Zhong-Qun Tian and Xue-Min Zhang 7.1 Early History of Electrochemical Surface-Enhanced Raman Spectroscopy 116 7.2 Principles and Methods of SERS 117 7.2.1 Electromagnetic Enhancement of SERS 118 7.2.2 Key Factors Influencing SERS 119 7.2.3 “Borrowing SERS Activity” Methods 121 7.2.4 Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy 123 7.3 Features of EC-SERS 124 7.3.1 Electrochemical Double Layer of EC-SERS Systems 124 7.3.2 Electrolyte Solutions and Solvent Dependency 125 7.4 EC-SERS Experiments 125 7.4.1 Measurement Procedures for EC-SERS 125 7.4.2 Experimental Set-Up for EC-SERS 127 7.4.3 Preparation of SERS Substrates 128 Acknowledgments 131 References 131 8 Applications of Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS) 137 Marco Musiani, Jun-Yang Liu and Zhong-Qun Tian 8.1 Pyridine Adsorption on Different Metal Surfaces 138 8.2 Interfacial Water on Different Metals 141 8.3 Coadsorption of Thiourea with Inorganic Anions 143 8.4 Electroplating Additives 146 8.5 Inhibition of Copper Corrosion 147 8.6 Extension of SERS to the Corrosion of Fe and Its Alloys: Passivity 149 8.6.1 Fe-on-Ag 150 8.6.2 Ag-on-Fe 150 8.7 SERS of Corrosion Inhibitors on Bare Transition Metal Electrodes 150 8.8 Lithium Batteries 152 8.9 Intermediates of Electrocatalysis 154 Acknowledgments 156 References 156 9 In-Situ Scanning Probe Microscopies: Imaging and Beyond 163 Bing-Wei Mao 9.1 Principle of In-Situ STM and In-Situ AFM 164 9.1.1 Principle of In-Situ STM 164 9.1.2 Principle of In-Situ AFM 166 9.2 In-Situ STM Characterization of Surface Electrochemical Processes 167 9.2.1 In-Situ STM Study of Electrode–Aqueous Solution Interfaces 167 9.2.2 In-Situ STM Study of Electrode–Ionic Liquid Interface 167 9.3 In-Situ AFM Probing of Electric Double Layer 170 9.4 Electrochemical STM Break-Junction for Surface Nanostructuring and Nanoelectronics and Molecular Electronics 173 9.5 Outlook 176 References 177 10 In-Situ Infrared Spectroelectrochemical Studies of the Hydrogen Evolution Reaction 183 Richard J. Nichols 10.1 The H+/H2 Couple 183 10.2 Single-Crystal Surfaces 184 10.3 Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy 186 10.4 Surface-Enhanced Raman Spectroscopy 189 10.5 Surface-Enhanced IR Absorption Spectroscopy 190 10.6 In-Situ Sum Frequency Generation Spectroscopy 193 10.7 Spectroscopy at Single-Crystal Surfaces 194 10.8 Overall Conclusions 197 References 198 11 Electrochemical Noise: A Powerful General Tool 201 Claude Gabrielli and David E. Williams 11.1 Instrumentation 202 11.2 Applications 204 11.2.1 Elementary Phenomena 204 11.2.2 Bioelectrochemistry 205 11.2.3 Electrocrystallization 207 11.2.4 Corrosion 209 11.2.5 Other Systems 215 11.3 Conclusions 217 References 217 12 From Microelectrodes to Scanning Electrochemical Microscopy 223 Salvatore Daniele and Guy Denuault 12.1 The Contribution of Microelectrodes to Electroanalytical Chemistry 224 12.1.1 Advantages of Microelectrodes in Electroanalysis 224 12.1.2 Microelectrodes and Electrode Materials 226 12.1.3 New Applications of Microelectrodes in Electroanalysis 227 12.2 Scanning Electrochemical Microscopy (SECM) 230 12.2.1 A Brief History of SECM 230 12.2.2 SECM with Other Techniques 231 12.2.3 Tip Geometries and the Need for Numerical Modeling 233 12.2.4 Applications of SECM 234 12.3 Conclusions 235 References 235 13 Cold Fusion After A Quarter-Century: The Pd/D System 245 Melvin H. Miles and Michael C.H. McKubre 13.1 The Reproducibility Issue 247 13.2 Palladium–Deuterium Loading 247 13.3 Electrochemical Calorimetry 249 13.4 Isoperibolic Calorimetric Equations and Modeling 250 13.5 Calorimetric Approximations 251 13.6 Numerical Integration of Calorimetric Data 252 13.7 Examples of Fleischmann’s Calorimetric Applications 254 13.8 Reported Reaction Products for the Pd/D System 256 13.8.1 Helium-4 256 13.8.2 Tritium 256 13.8.3 Neutrons, X-Rays, and Transmutations 257 13.9 Present Status of Cold Fusion 257 Acknowledgments 258 References 258 14 In-Situ X-Ray Diffraction of Electrode Surface Structure 261 Andrea E. Russell, Stephen W.T. Price and Stephen J. Thompson 14.1 Early Work 262 14.2 Synchrotron-Based In-Situ XRD 264 14.3 Studies Inspired by Martin Fleischmann’s Work 266 14.3.1 Structure of Water at the Interface 266 14.3.2 Adsorption of Ions 268 14.3.3 Oxide/Hydroxide Formation 268 14.3.4 Underpotential Deposition (upd) of Monolayers 270 14.3.5 Reconstructions of Single-Crystal Surfaces 275 14.3.6 High-Surface-Area Electrode Structures 275 14.4 Conclusions 277 References 277 15 Tribocorrosion 281 Robert J.K. Wood 15.1 Introduction and Definitions 281 15.1.1 Tribocorrosion 282 15.1.2 Erosion 282 15.2 Particle–Surface Interactions 283 15.3 Depassivation and Repassivation Kinetics 283 15.3.1 Depassivation 284 15.3.2 Repassivation Rate 286 15.4 Models and Mapping 287 15.5 Electrochemical Monitoring of Erosion–Corrosion 290 15.6 Tribocorrosion within the Body: Metal-on-Metal Hip Joints 291 15.7 Conclusions 293 Acknowledgments 293 References 293 16 Hard Science at Soft Interfaces 295 Hubert H. Girault 16.1 Charge Transfer Reactions at Soft Interfaces 295 16.1.1 Ion Transfer Reactions 296 16.1.2 Assisted Ion Transfer Reactions 298 16.1.3 Electron Transfer Reactions 299 16.2 Electrocatalysis at Soft Interfaces 300 16.2.1 Oxygen Reduction Reaction (ORR) 301 16.2.2 Hydrogen Evolution Reaction (HER) 302 16.3 Micro- and Nano-Soft Interfaces 304 16.4 Plasmonics at Soft Interfaces 305 16.5 Conclusions and Future Developments 305 References 307 17 Electrochemistry in Unusual Fluids 309 Philip N. Bartlett 17.1 Electrochemistry in Plasmas 310 17.2 Electrochemistry in Supercritical Fluids 314 17.2.1 Applications of SCF Electrochemistry 321 17.3 Conclusions 325 Acknowledgments 325 References 325 18 Aspects of Light-Driven Water Splitting 331 Laurence Peter 18.1 A Very Brief History of Semiconductor Electrochemistry 332 18.2 Thermodynamic and Kinetic Criteria for Light-Driven Water Splitting 334 18.3 Kinetics of Minority Carrier Reactions at Semiconductor Electrodes 336 18.4 The Importance of Electron–Hole Recombination 338 18.5 Fermi Level Splitting in the Semiconductor–Electrolyte Junction 339 18.6 A Simple Model for Light-Driven Water-Splitting Reaction 341 18.7 Evidence for Slow Electron Transfer During Light-Driven Water Splitting 343 18.8 Conclusions 345 Acknowledgments 345 References 346 19 Electrochemical Impedance Spectroscopy 349 Samin Sharifi-Asl and Digby D. Macdonald 19.1 Theory 350 19.2 The Point Defect Model 350 19.2.1 Calculation of Y0F 355 19.2.2 Calculation of ΔC0 i ΔU 355 19.2.3 Calculation of ΔCL v ΔU 356 19.3 The Passivation of Copper in Sulfide-Containing Brine 357 19.4 Summary and Conclusions 363 Acknowledgments 363 References 363 Index 367

Rezension

“The high quality chapters presented in this volume contribute greatly to achieving the editors’ goal.” (Chromatographia, 1 May 2015)

Autorenportrait

Derek Pletcher is Emeritus Professor at the University of Southampton. His research interests extend from fundamental electrochemistry, through electrochemical engineering to the industrial applications of electrolysis. He is the author of ~ 340 technical papers and ~ 30 reviews and has supervised the training of more than 90 postgraduate students. In 2010, he was awarded the prestigious Vittorio de Nora Medal by the US Electrochemical Society for his work related to the applications of electrochemistry. He is an elected Fellow of the Electrochemical Society (2005) and was awarded their Henry Linford Medal for Teaching Excellence in Electrochemistry (2006). He is a past Editor of the Journal of Applied Electrochemistry (1980 - 85) and presently serves on the Editorial Boards of Electrochimica Acta and Electrochemical Communications. Zhong-Qun Tian heads the Surface-enhanced Raman Spectroscopy and Nano-electrochemistry research group at Xiamen University. He graduated from the Department of Chemistry at Xiamen University in 1982 with a BSc and received his Ph.D in 1987 under advisor, Martin Fleischmann, FRS. He is a Fellow of International Society of Electrochemistry (ISE), 2010- ;Regional Representative (China) of International Society of Electrochemistry (ISE), 2007-2009; Fellow of Royal Society of Chemistry, UK, 2005- ; Council Member of Chinese Society of Micro/Nano Technology, 2005-; Guest Professor of Chemistry, Chinese University of Hong Kong, China, 2006-; Guest Professor of Chemistry, Univ. of Science and Technology of China, China, 2001-; Visiting Professor of Ecole Normal Superior, Paris, France, 2008/9. He has over 310 papers, five chapters in encyclopaedias and books and has edited two special journal issues. David Williams is Professor of Electrochemistry at the University of Auckland, NZ. His research covers electrochemistry and corrosion science. He is a graduate of the University of Auckland and developed his research career in electrochemistry and chemical sensors at the UK Atomic Energy Research Establishment, in the 1980s. He became Thomas Graham Professor of Chemistry at UCL in 1991. He joined the faculty of the Chemistry Dept at Auckland University in 2006. He is an Adjunct Professor at Dublin City University. He is a Visiting Professor at UCL, and University of Southampton, and Honorary Professor of the Royal Institution of Great Britain. He has published around 200 papers in international journals, and is the inventor of around 40 patents.

Back cover copy

Martin Fleischmann was truly one of the ‘fathers’ of modern electrochemistry having made major contributions to diverse topics within electrochemical science and technology. These include the theory and practice of voltammetry and in situ spectroscopic techniques, instrumentation, electrochemical phase formation, corrosion, electrochemical engineering, electrosynthesis and cold fusion. While intended to honour the memory of Martin Fleischmann, this book is neither a biography nor a history of his contributions. Rather, it is a series of critical reviews of topics in electrochemical science associated with Martin Fleischmann but remaining important today. The authors are all scientists with outstanding international reputations who have made their own contribution to their topic; most have also worked with Martin Fleischmann and benefitted from his guidance. Each of the 19 chapters within this volume begin with an outline of Martin Fleischmann’s contribution to the topic, followed by examples of research, established applications and prospects for future developments. The book will be of interest to both students and experienced workers in universities and industry who are active in developing electrochemical science.