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Full Description
The objective of the present volume is to develop the theory and practice of nonmetal electrochemistry from first principles, emphasizing energy level models, in particular the fluctuating energy level model of Marcus and Gerischer. A single volume emphasizing these models. and the in terpretation of experiments based on these models, has not been available. Yet this area of electrochemical technology, where the use of such models is required, has developed a great deal of interest. This is not only because of the interest in photoelectrochemical solar cells, but also because of the importance of the concepts in corrosion, sensors, coated metal electrodes, and, indeed, to the general theory of electrode reactions. This book is an attempt to fill the void-to develop in a single volume the basic description of electrode reactions on nonmetallic electrodes and oxide-covered metal electrodes. The development of the fluctuating energy level model to describe electrode reactions on nonmetals (as described in Chapters I through 3) has permitted a significant forward step in the understanding of such re actions. The power of the model is illustrated by the simple methods available to determine the energy levels of interest-the conduction and valence bands of the nonmetals (Chapter 5), and their relation to the energy levels of oxidizing or reducing agents in solution. In Chapter 6, we illustrate the ability of the simple models. based on these parameters, to describe successfully electrode reactions at an inert electrode.
Contents
1. The Solid and the Solution.- 1.1. The Solid.- 1.2. The Solution.- 2. The Solid/Liquid Interface.- 2.1. Surface Ions and Their Energy Levels.- 2.2. Double Layers at the Solid/Liquid Interface.- 2.3. Theoretical Predictions of the Energy Levels of Band Edges.- 2.4. The Band Model of the Solid/Solution Interface.- 3. Theory of Electron and Hole Transfer.- 3.1. Introduction.- 3.2. Classical Model.- 3.3. The Energy Level Model of Charge Transfer.- 3.4. Qualitative Description of Electrode Processes Using the Band Model.- 4. Measurement Techniques.- 4.1. Capacity Measurements.- 4.2. Measurements of the Current/Voltage Characteristics.- 4.3. Other Techniques.- 5. The Properties of the Electrode and Their Effect on Electrochemical Measurements.- 5.1. The Behavior of the Perfect Crystal.- 5.2. The Behavior of Electrode Defects.- 5.3. Observed Flat Band Potentials for Various Semiconductors.- 6. Observations of Charge Transfer at an Inert Semiconductor Electrode.- 6.1. Introduction.- 6.2. Majority Carrier Capture.- 6.3. Minority Carrier Capture.- 6.4. Intrinsic Surface States and Recombination Centers.- 6.5. Carrier Injection.- 6.6. High-Current, High-Voltage Processes.- 6.7. Analysis of Complicated Electrode Reactions using the Tools of Semiconductor Electrochemistry.- 7. Chemical Transformation in the Electrode Reaction.- 7.1. Introduction.- 7.2. Inner Sphere Changes during Redox Reactions at an Inert Electrode.- 7.3. Adsorption onto and Absorption into the Electrode.- 7.4. Corrosion.- 8. Coated Electrodes.- 8.1. Introduction.- 8.2. Current Transport through Oxide Films.- 8.3. Deposition of Reaction Products on Semiconductor Electrodes.- 9. Applications of Semiconductor Electrodes.- 9.1. Solar Energy Conversion.- 9.2. Electrocatalysis on Semiconductors.- 9.3. New Devices.- 9.4. Electropolishing of Semiconductors.- References.- References to Review Articles and Books.- Author Index.
