Developments in Electrochemistry

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.

• List of Contributors xiii1 Martin Fleischmann – The Scientist and the Person 12 A Critical Review of the Methods Available for Quantitative Evaluation of Electrode Kinetics at Stationary Macrodisk Electrodes 21Alan M. Bond, Elena A. Mashkina and Alexandr N. Simonov2.1 DC Cyclic Voltammetry 232.1.1 Principles 232.1.2 Processing DC Cyclic Voltammetric Data 262.1.3 Semiintegration 292.2 AC Voltammetry 322.2.1 Advanced Methods of Theory–Experiment Comparison 352.3 Experimental Studies 362.3.1 Reduction of [Ru(NH3)6]3+ in an Aqueous Medium 362.3.2 Oxidation of FeII(C5H5)2 in an Aprotic Solvent 402.3.3 Reduction of [Fe(CN)6]3− in an Aqueous Electrolyte 422.4 Conclusions and Outlook 43References 453 Electrocrystallization: Modeling and Its Application 49Morteza Y. Abyaneh3.1 Modeling Electrocrystallization Processes 533.2 Applications of Models 563.2.1 The Deposition of Lead Dioxide 583.2.2 The Electrocrystallization of Cobalt 603.3 Summary and Conclusions 61References 634 Nucleation and Growth of New Phases on Electrode Surfaces 65Benjamin R. Scharifker and Jorge Mostany4.1 An Overview of Martin Fleischmann’s Contributions to Electrochemical Nucleation Studies 664.2 Electrochemical Nucleation with Diffusion-Controlled Growth 674.3 Mathematical Modeling of Nucleation and Growth Processes 684.4 The Nature of Active Sites 694.5 Induction Times and the Onset of Electrochemical Phase Formation Processes 714.6 Conclusion 72References 725 Organic Electrosynthesis 77Derek Pletcher5.1 Indirect Electrolysis 795.2 Intermediates for Families of Reactions 805.3 Selective Fluorination 845.4 Two-Phase Electrolysis 855.5 Electrode Materials 875.6 Towards Pharmaceutical Products 885.7 Future Prospects 90References 916 Electrochemical Engineering and Cell Design 95Frank C. Walsh and Derek Pletcher6.1 Principles of Electrochemical Reactor Design 966.1.1 Cell Potential 966.1.2 The Rate of Chemical Change 976.2 Decisions During the Process of Cell Design 986.2.1 Strategic Decisions 986.2.2 Divided and Undivided Cells 986.2.3 Monopolar and Bipolar Electrical Connections to Electrodes 996.2.4 Scaling the Cell Current 1006.2.5 Porous 3D Electrode Structures 1006.2.6 Interelectrode Gap 1016.3 The Influence of Electrochemical Engineering on the Chlor-Alkali Industry 1026.4 Parallel Plate Cells 1056.5 Redox Flow Batteries 1066.6 Rotating Cylinder Electrode Cells 1076.7 Conclusions 108References 1097 Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS): Early History, Principles, Methods, and Experiments 113Zhong-Qun Tian and Xue-Min Zhang7.1 Early History of Electrochemical Surface-Enhanced Raman Spectroscopy 1167.2 Principles and Methods of SERS 1177.2.1 Electromagnetic Enhancement of SERS 1187.2.2 Key Factors Influencing SERS 1197.2.3 “Borrowing SERS Activity” Methods 1217.2.4 Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy 1237.3 Features of EC-SERS 1247.3.1 Electrochemical Double Layer of EC-SERS Systems 1247.3.2 Electrolyte Solutions and Solvent Dependency 1257.4 EC-SERS Experiments 1257.4.1 Measurement Procedures for EC-SERS 1257.4.2 Experimental Set-Up for EC-SERS 1277.4.3 Preparation of SERS Substrates 128Acknowledgments 131References 1318 Applications of Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS) 137Marco Musiani, Jun-Yang Liu and Zhong-Qun Tian8.1 Pyridine Adsorption on Different Metal Surfaces 1388.2 Interfacial Water on Different Metals 1418.3 Coadsorption of Thiourea with Inorganic Anions 1438.4 Electroplating Additives 1468.5 Inhibition of Copper Corrosion 1478.6 Extension of SERS to the Corrosion of Fe and Its Alloys: Passivity 1498.6.1 Fe-on-Ag 1508.6.2 Ag-on-Fe 1508.7 SERS of Corrosion Inhibitors on Bare Transition Metal Electrodes 1508.8 Lithium Batteries 1528.9 Intermediates of Electrocatalysis 154Acknowledgments 156References 1569 In-Situ Scanning Probe Microscopies: Imaging and Beyond 163Bing-Wei Mao9.1 Principle of In-Situ STM and In-Situ AFM 1649.1.1 Principle of In-Situ STM 1649.1.2 Principle of In-Situ AFM 1669.2 In-Situ STM Characterization of Surface Electrochemical Processes 1679.2.1 In-Situ STM Study of Electrode–Aqueous Solution Interfaces 1679.2.2 In-Situ STM Study of Electrode–Ionic Liquid Interface 1679.3 In-Situ AFM Probing of Electric Double Layer 1709.4 Electrochemical STM Break-Junction for Surface Nanostructuring and Nanoelectronics and Molecular Electronics 1739.5 Outlook 176References 17710 In-Situ Infrared Spectroelectrochemical Studies of the Hydrogen Evolution Reaction 183Richard J. Nichols10.1 The H+/H2 Couple 18310.2 Single-Crystal Surfaces 18410.3 Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy 18610.4 Surface-Enhanced Raman Spectroscopy 18910.5 Surface-Enhanced IR Absorption Spectroscopy 19010.6 In-Situ Sum Frequency Generation Spectroscopy 19310.7 Spectroscopy at Single-Crystal Surfaces 19410.8 Overall Conclusions 197References 19811 Electrochemical Noise: A Powerful General Tool 201Claude Gabrielli and David E. Williams11.1 Instrumentation 20211.2 Applications 20411.2.1 Elementary Phenomena 20411.2.2 Bioelectrochemistry 20511.2.3 Electrocrystallization 20711.2.4 Corrosion 20911.2.5 Other Systems 21511.3 Conclusions 217References 21712 From Microelectrodes to Scanning Electrochemical Microscopy 223Salvatore Daniele and Guy Denuault12.1 The Contribution of Microelectrodes to Electroanalytical Chemistry 22412.1.1 Advantages of Microelectrodes in Electroanalysis 22412.1.2 Microelectrodes and Electrode Materials 22612.1.3 New Applications of Microelectrodes in Electroanalysis 22712.2 Scanning Electrochemical Microscopy (SECM) 23012.2.1 A Brief History of SECM 23012.2.2 SECM with Other Techniques 23112.2.3 Tip Geometries and the Need for Numerical Modeling 23312.2.4 Applications of SECM 23412.3 Conclusions 235References 23513 Cold Fusion After A Quarter-Century: The Pd/D System 245Melvin H. Miles and Michael C.H. McKubre13.1 The Reproducibility Issue 24713.2 Palladium–Deuterium Loading 24713.3 Electrochemical Calorimetry 24913.4 Isoperibolic Calorimetric Equations and Modeling 25013.5 Calorimetric Approximations 25113.6 Numerical Integration of Calorimetric Data 25213.7 Examples of Fleischmann’s Calorimetric Applications 25413.8 Reported Reaction Products for the Pd/D System 25613.8.1 Helium-4 25613.8.2 Tritium 25613.8.3 Neutrons, X-Rays, and Transmutations 25713.9 Present Status of Cold Fusion 257Acknowledgments 258References 25814 In-Situ X-Ray Diffraction of Electrode Surface Structure 261Andrea E. Russell, Stephen W.T. Price and Stephen J. Thompson14.1 Early Work 26214.2 Synchrotron-Based In-Situ XRD 26414.3 Studies Inspired by Martin Fleischmann’s Work 26614.3.1 Structure of Water at the Interface 26614.3.2 Adsorption of Ions 26814.3.3 Oxide/Hydroxide Formation 26814.3.4 Underpotential Deposition (upd) of Monolayers 27014.3.5 Reconstructions of Single-Crystal Surfaces 27514.3.6 High-Surface-Area Electrode Structures 27514.4 Conclusions 277References 27715 Tribocorrosion 281Robert J.K. Wood15.1 Introduction and Definitions 28115.1.1 Tribocorrosion 28215.1.2 Erosion 28215.2 Particle–Surface Interactions 28315.3 Depassivation and Repassivation Kinetics 28315.3.1 Depassivation 28415.3.2 Repassivation Rate 28615.4 Models and Mapping 28715.5 Electrochemical Monitoring of Erosion–Corrosion 29015.6 Tribocorrosion within the Body: Metal-on-Metal Hip Joints 29115.7 Conclusions 293Acknowledgments 293References 29316 Hard Science at Soft Interfaces 295Hubert H. Girault16.1 Charge Transfer Reactions at Soft Interfaces 29516.1.1 Ion Transfer Reactions 29616.1.2 Assisted Ion Transfer Reactions 29816.1.3 Electron Transfer Reactions 29916.2 Electrocatalysis at Soft Interfaces 30016.2.1 Oxygen Reduction Reaction (ORR) 30116.2.2 Hydrogen Evolution Reaction (HER) 30216.3 Micro- and Nano-Soft Interfaces 30416.4 Plasmonics at Soft Interfaces 30516.5 Conclusions and Future Developments 305References 30717 Electrochemistry in Unusual Fluids 309Philip N. Bartlett17.1 Electrochemistry in Plasmas 31017.2 Electrochemistry in Supercritical Fluids 31417.2.1 Applications of SCF Electrochemistry 32117.3 Conclusions 325Acknowledgments 325References 32518 Aspects of Light-Driven Water Splitting 331Laurence Peter18.1 A Very Brief History of Semiconductor Electrochemistry 33218.2 Thermodynamic and Kinetic Criteria for Light-Driven Water Splitting 33418.3 Kinetics of Minority Carrier Reactions at Semiconductor Electrodes 33618.4 The Importance of Electron–Hole Recombination 33818.5 Fermi Level Splitting in the Semiconductor–Electrolyte Junction 33918.6 A Simple Model for Light-Driven Water-Splitting Reaction 34118.7 Evidence for Slow Electron Transfer During Light-Driven Water Splitting 34318.8 Conclusions 345Acknowledgments 345References 34619 Electrochemical Impedance Spectroscopy 349Samin Sharifi-Asl and Digby D. Macdonald19.1 Theory 35019.2 The Point Defect Model 35019.2.1 Calculation of Y0F 35519.2.2 Calculation of ΔC0 i ΔU 35519.2.3 Calculation of ΔCL v ΔU 35619.3 The Passivation of Copper in Sulfide-Containing Brine 35719.4 Summary and Conclusions 363Acknowledgments 363References 363Index 367

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