Modern Aspects of Electrochemistry: Volume 17

ISBN-13: 9781461292609 / Angielski / Miękka / 2011 / 508 str.

Brian E. Conway; John O'm Bockris;Ralph E. White

Opis

It gives us pleasure in writing the Preface to this volume, in which we tried to bring together a number of stimulating and interesting people discussing physical electrochemistry. The first chapter, by Ashok Vijh, gives a remarkable account of electrochemistry as looked at from a physicist's point of view. Among the revelations of the chapter is that in a recent survey of leading areas in Science, two out of fifteen areas chosen were electrochemical and these two were the only chemical subjects chosen. In Mikhail Vorotyntsev's chapter, one finds a very modern study of the double layer, but tenuously connected with the simpler studies made in the safe harbor of mercury. In the pioneering chapter by Pons et al., one is looking at a cutting edge of electrochemistry at this time-the use of IR spectros- copy in modes which allow the first practical determinations of the spectra of adsorbed species at the interface-an area pioneered by Pons himself. In Chapter 4, we have reached photoelectrochemistry once more, but now Tributsch speaks about what has rapidly become the major area of that topic, photoelectrocatalysis. Close to this chapter, and indeed intellectually connected with it, is that by Schmickler and Schultze about electron transfer reac- tions at oxide-covered metal electrodes in which theories which are still relatively dubious for metal-solution surfaces are applied to complex systems involving oxides.

Spis treści

1 Perspectives in Electrochemical Physics.- I. Introduction.- II. Importance of Electrochemical Physics.- 1. Scope.- 2. Origins and Evolution.- 3. Current Scientific Importance.- III. Electrocatalysis by Metals and Alloys.- 1. Electrocatalysis of the h.e.r. and the Electronic Structure of Metals.- 2. Volcano Plots.- 3. The Current Experimental Situation of the Catalysis of Various Electrode Reactions.- IV. Electrode Reactions on Semiconductors.- 1. General.- 2. Simple Ion Transfer.- 3. Redox Reactions.- 4. Photoelectrochemical Reactions and Cells.- 5. Some Materials Problems in Photoelectrochemical Cells.- V. Solid-State Properties and Electrochemical Behavior: Corrosion, Anodic Dissolution, and Oxide Growth.- 1. General.- 2. The M?Mz+ + ze Reaction.- 3. Anodic Dissolution of Some Film-Covered Electrodes.- 4. The Fretting Corrosion of Metals.- 5. The Pitting Potentials of Metals.- 6. The Passivation of Metals in an Aggressive Electrolyte.- 7. Open-Circuit Corrosion and “Chemical” Dissolution.- 8. Anodic Oxide Growth and Metal/Oxide Electrodes.- VI. Electrochemical Physics of Metal/ Dielectric Interfaces.- 1. The Open-Circuit Voltages in Metal-Polymer-Metal Systems.- 2. The Nature of Metal/SF6 Reactions Accompanying the Passage of Direct Current across the Interface.- 3. The Electrical Signals at Metal Electrodes in Nitromethane During Detonation: Electrochemical Basis.- 4. Solid-State Electrochemistry of Dielectric Breakdown in Alkali Halides.- 5. Some Other Electrochemical Problems at Metal/Media Interfaces.- VII. Metal-Plasma (“Gaseous Electrolyte”) Interfaces.- 1. Electrochemical Physics of the Metal-Plasma Interface.- 2. Electrode Potentials Appropriate to the Cathode Fall Region.- 3. Estimation of the Surface Plasmon Energies of Metals.- VIII. Synopses of Work on Other Themes and Subjects.- 1. Quantum Electrochemistry.- 2. Electrochemical Physics in Biology.- 3. Solid Electrolytes.- 4. Electrochemical Materials Science.- 5. Miscellaneous Other Work.- References.- 2 Modern State of Double Layer Study of Solid Metals.- I. Introduction.- II. Double Layer Structure at Liquid Metals and Alloys.- III. The Gouy-Chapman-Stern-Grahame (GCSG) Theory for “Uniform” Solid Electrodes.- IV. Capacitance Characteristics of Solid Polycrystalline (PC) Electrodes.- 1. Preliminary Notes.- 2. Lead.- 3. Bismuth.- 4. Thallium.- 5. Antimony.- 6. Cadmium.- 7. Tin.- 8. Solid Gallium.- 9. Indium.- 10. Zinc.- 11. Copper.- 12. Silver.- 13. Gold.- V. Capacitance Characteristics of Individual Single-Crystal Faces.- 1. Introduction.- 2. Metals with a Small Difference of PZC of the Faces.- 3. Metal Faces with a Considerable Difference of their PZC.- VI. Crystallographic Inhomogeneity Effects.- VII. Conclusion.- References.- 3 Interfacial Infrared Vibrational Spectroscopy.- I. Introduction.- II. Theoretical Considerations and Experimental Techniques.- 1. Surface Selection Rule.- 2. The Spectroelectrochemical Cell.- 3. SNIFTIRS Technique.- 4. EMIRS Technique.- 5. Form of the Spectra.- 6. Polarization Modulated IRRAS Technique.- III. Applications.- 1. Electrocatalytic Reactions.- 2. Molecular Adsorption.- 3. Ion Radical Intermediates.- 4. Adsorption of Ions.- IV. Future Directions.- References.- 4 Photoelectrolysis and Photoelectrochemical Catalysis.- I. Introduction.- 1. Thermodynamics of Photoelectrolysis.- 2. Kinetic Considerations.- 3. Evaluation of Research in Photoelectrolysis.- II. Photoelectrochemistry of d-Band Sulfides.- 1. Photoelectrocatalytic Properties of TS2 Compounds.- 2. Surface States in d-Band Sulfides.- 3. Catalytic Limitations of Transition Metal Disulfides.- III. Tailoring Reactive Surface States for Photoelectrocatalysis.- 1. Theoretical Concepts of Pools for Electrons and Holes.- 2. Analogy with Hydrodesulfurization Catalysis.- 3. Towards a Photoelectrochemistry of Semiconducting Cluster Compounds.- 4. Advantages of Cooperative Mechanisms Involving Transition Metal Clusters.- IV. Experiments Using Semiconductor Electrodes with Paired and Clustered Transition Metals.- 1. Materials with Clustered Metals.- 2. Photoelectrochemistry of RuP3 with Ru Pairs.- 3. Photoelectrodes with Clustered Transition Metals.- V. Discussion.- References.- 5 Electron Transfer Reactions on Oxide-Covered Metal Electrodes.- I. Introduction.- II. Experimental Problems.- 1. Preparation of Oxide Films.- 2. Structure of the Films.- 3. Nonstoichiometry and Impurities.- 4. Films on Alloys.- 5. The Oxide-Electrolyte Interface.- III. The Metal-Passive Film-Redox Electrolyte Interface.- 1. Band Structure of a Passive Film.- 2. Electronic Equilibrium Condition for the Interface.- 3. Potential Variation and Band Bending.- 4. Band Structure of Some Oxide Films.- IV. Mechanisms of Electron Transfer at Film-Covered Electrodes.- 1. Electron Exchange with the Metal.- 2. Electron Exchange with the Film.- 3. Experimental Mechanism Criteria.- V. Discussion of Some Particular Systems.- 1. Passive Titanium Electrodes.- 2. Passive Tin.- 3. Passive Niobium Electrodes.- 4. Oxygen Evolution on Passive Platinum.- 5. Passive Gold.- 6. Passive Iron.- 7. Sandwich Oxides.- VI. Exchange Current Densities and Electronic Properties.- References.- 6 Interfacial Electrostatics and Electrodynamics in Disperse Systems.- I. Introduction.- II. Interfacial Electrostatics.- 1. Origin of Charges and Potentials.- 2. Determination of the Surface Charge.- 3. Thermodynamics.- 4. Information from the Colloidal Side.- 5. Points of Zero Charge and Isoelectric Points.- 6. Examples of Double Layer Studies: Silver Iodide.- 7. Examples of Double Layer Studies: Oxides.- III. Interfacial Electrodynamics.- 1. Types of Approach.- 2. Theory of Double Layer Relaxation.- 3. Assessment of Kinetic Double Layer Parameters.- 4. Relaxation and Colloid Stability.- IV. Conclusion and Summary.- References.