Costas G. Vayenas - Böcker

This work describes the phenomenology, theory and potential applications of the phenomenon of electrochemical promotion, where electrochemically induced ion spillover activates and controls heterogeneous catalysis. The origin of electrochemical promotion is discussed in light of a plethora of surface spectroscopic and electrochemical techniques. Electrochemical and classical promotion are compared, their common rules are identified and promotional kinetics are rigorously modelled and compared with experiment.

This text explores several aspects of electrochemistry. It includes a chapter on electrochemical nuclear magnetic resonance (EC-NMR) - a powerful non-invasive technique which brings insights to both fundamental and practical key aspects of electrocatalysis, including the design of better anodes for PEM fuel cells. There is also a chapter devoted to advances in the use of rigorous ab initio quantum chemical calculations in electrochemistry, addressed to all electrochemists, including those with very little prior exposure to quantum chemistry, and demonstrates the usefulness of ab initio calculations, including density functional theory (DFT) methods, to understand several key aspects of fuel cell electrocatalysis at the molecular level.The text also discusses the most important macroscopic and statistical thermodynamic models developed to describe adsorption phenomena on electrodes, including the state of the art adsorption isotherms, which are both rigorous, and in good agreement with experiment, as well as electrochemical promotion - the use of electrochemistry to activate and in situ tune the catalytic activity and selectivity of metal and metal oxide catalysts interfaced with solid electrolytes.

Topics discussed include: Solid State Electrochemistry, Kinetics of Electrochemical Hydrogen Entry into Metals and Alloys, Electrochemistry of Titanium, Electrochemical Oxidation of Organics on Synthetic Diamond-based Electrodes, Fuel Cells, Trace-Anion Catalysis of Outer-Sphere Heterogeneous Charge-Transfer Reactions, Thermodynamic and Transport Properties of Bridging Electrolyte - Water Systems Hydrogen, diamond electrodes, and fuel cells were all topics of intense interest at the 2003 ECS meeting in Paris.

Topics in Number 36 include: *Electrochemical nuclear magnetic resonance (EC-NMR). This powerful non-invasive technique brings new insights to both fundamental and practical key aspects of electrocatalysis, including the design of better anodes for PEM fuel cells. *The recent impressive advances in the use of rigorous ab initio quantum chemical calculations in electrochemistry. This lucid chapter is addressed to all electrochemists, including those with very little prior exposure to quantum chemistry, and demonstrates the usefulness of ab initio calculations, including density functional theory (DFT) methods, to understand several key aspects of fuel cell electrocatalysis at the molecular level. *The most important macroscopic and statistical thermodynamic models developed to describe adsorption phenomena on electrodes, including the current state of the art adsorption isotherms, which are both rigorous, and in good agreement with experiment. *Electrochemical promotion i.e., the use of electrochemistry to activate and in situ tune the catalytic activity and selectivity of metal and metal oxide catalysts interfaced with solid electrolytes.*Lithium transport through transition metal oxides and carbonaceous materials, which is of paramount importance in rechargeable lithium batteries.

This volume of Modern Aspects contains seven chapters. The major topics covered in the first six chapters of this volume include fundamentals of solid state electrochemistry; kinetics of electrochemical hydrogen entry into metals and alloys; oxidation of organics; fuel cells; electrode kinetics of trace-anion catalysis; nano structural analysis. The last chapter is a corrected version of chapter four from Volume 35. Faisal M. AI-faqeer and Howard W. Pickering begin the first chapter by going back to 1864 and Cailletet who found that some hydrogen evolved and was absorbed by iron when it was immersed in dilute sulfuric acid. The absorption of hydrogen into metals and alloys can lead to catastrophic failures of structures. They discuss the kinetics of electrochemical hydrogen entry into metals and alloys. In chapter three, Clyde L. Briant reviews the electrochemistry, corrosion and hydrogen embrittlement of unalloyed titanium. He begins by reviewing the basic electrochemistry and general corrosion of titanium. He also discusses pitting and galvanostatic corrosion followed by a review of hydrogen embrittlement emphasizing the formation of hydrides and the effect of these on titanium's mechanical properties. Christos Comninellis and Gy6rgy F6ti discuss the oxidative electrochemical processes of organics in chapter three. They begin by defining direct and indirect electrochemical oxidation of organics. They introduce a model that allows them to distinguish between active (strong) and non-active (weak) anodes. Different classes of organic compounds are used for kinetic models of organic oxidation at active and non-active type anodes.