Photoelectrochemistry

ISBN-13: 9781461339328 / Angielski / Miękka / 2011 / 240 str.

Yu Gurevich

Opis

We enthusiastically welcome this opportunity to introduce this major work of Gurevich, Pleskov, and Rotenberg to English-speaking readers since photoelectrochemistry has, in recent years, become very significant for modern energy transfer and energy conversion phenomena. While having its roots in early electrochemistry, this field, in its modern aspects, has had an important impact on knowledge of the production and state of solvated electrons and on photoassisted electrolysis at semiconductors. Photoeffects resulting in electron emission into solution have also given rise to new ways of understanding double-layer structure and measuring potentials of zero charge. Electrochemical photoemission studies have added to and comple mented the literature of solvated electron chemistry arising from experiments with high-energy radiation. The authors' treatment of photoelectron emission phenomena at metal/ solution interfaces is thorough and quantitative and, we believe, will con stitute a landmark in the development of this fundamentally interesting and practically important area of electrochemistry and photophysics. H. Wroblowa B. E. Conway v Foreword A characteristic feature of modern electrochemistry is the continually broadening utilization of nontraditional methods and development of new directions of research. A number of such approaches are based on illumina tion techniques. First, irradiation is used in electrochemistry mainly as a research tool. Mention should be made here of methods such as electro reflection, ellipsometry, internal reflection spectroscopy, interferometry of surface layers, and other techniques firmly established in experimental electrochemistry. Second, light directly affects electrode processes. In vestigation of the latter phenomenon is the subject of photoelectrochemistry.

Spis treści

0.1. Historical Background.- 0.2. Stages of Photoelectron Emission into Solution.- 0.3. General Features of Emission Phenomena in Electrochemical Systems.- 1. Fundamentals of the Theory of Photoelectron Emission from Metals into Solutions.- 1.1. Qualitative Description of the Phenomenon.- 1.2. The Threshold Approach to Photoemission.- 1.3. Calculation of the Photoemission Current.- 1.4. The 5/2 Power Law.- 1.5. The Effects of the Double Layer on the Photoemission.- 1.6. Dependence of the Photoemission Current on the Characteristics of the Irradiation.- 2. Theory of Photodiffusion Currents.- 2.1. Formulation of the Problem and Basic Relations.- 2.2. Stationary Photodiffusion Currents.- 2.3. Alternating Photodiffusion Currents.- 3. Experimental Techniques in Photoemission Studies.- 3.1. General Discussion of Photocurrent Measurements.- 3.2. Measuring Apparatus.- 3.3. Electrode Illumination.- 3.4. Electrochemical Cells.- 3.5. The Choice of Acceptors for Solvated Electrons.- 4. Photoelectron Emission in Solutions: Its Discovery, Kinetics, and Energetics.- 4.1. Introductory Notes.- 4.2. The Dependence of the Photoemission Current on the Electrode Potential and Quantum Energy. Experimental Verification of the 5/2 Power Law.- 4.3. The Effect of the Nature of the Metal on Photoemission and Electrochemical Kinetics.- 4.4. Energetics of Excess Electrons in Polar Solvents.- 4.5. The Effect of the Light Frequency and Polarization. Bulk andSurface Excitation of Electrons.- 4.6. Multiphoton Emission.- 5. Emitted Electrons in Solution: Subsequent Transformations.- 5.1. Dependence of the Photocurrent on Acceptor Concentration.- 5.2. Is There a Contribution of “Dry” Electrons to Photodiffusion Currents?.- 5.3. Characteristics of Retardation and Hydration of Photoelectrons.- 5.4. Slow Capture of Hydrated Electrons by the Metal Surface.- 5.5. Measurements of the Rate Constants of Electron Capture by Acceptors.- 5.6. Method of Competing Acceptors in Photoemission Studies.- 6. Investigation of the Structure of the Electric Double Layer Using the Photoemission Method.- 6.1. The Role of the Diffuse Layer in Photoemission Phenomena; General Considerations.- 6.2. Dependence of the Photocurrent on Electrolyte Concentration.- 6.3. Measurement of the Potential of Zero Charge by a Photoemission Method.- 6.4. Direct Experimental Determination of the ? Potential.- 6.5. Investigation of Specific Adsorption.- 6.6. Evaluation of the Thickness of the Compact Layer.- 7. Photoemission As a Method of Investigation of Electrochemical Kinetics: Processes Involving Atomic Hydrogen.- 7.1. Formation of Atomic Hydrogen in Electrochemical Reactions. Phenomenology and Empirical Equations.- 7.2. Basic Experimental Data Concerning Atomic Hydrogen Reactions.- 7.3. The Role of the Adsorption Stage.- 7.4. The Mechanism of Atomic Hydrogen Reactions on Mercury Electrodes.- 7.5. The Mechanism of Atomic Hydrogen Reactions at Bismuth and Other Solid Electrodes.- 7.6. The Effect of the Double Layer on the Kinetics of Atomic Hydrogen Reactions.- 8. Photoemission As a Method of Investigating Homogeneous Reactions Involving Free Radicals.- 8.1. Chemical and Electrochemical Reactions of the Radical Anion NO32-.- 8.2. Chemical and Electrochemical Reactions Involving CO2? and CH3° Radicals.- 8.3. Chemical Reactions of H and OH Radicals with Alcohols and Other Organic Compounds.- 8.4. Multielectron Electrochemical Reactions Initiated by Photoemission.- 9. Photoelectron Emission from Semiconductors into Solutions and from Solutions into the Vapor Phase.- 9.1. Qualitative Description of Photoemission from Semiconductors.- 9.2. Calculation of the Photoemission Current at Semiconductor Electrodes.- 9.3. Photoemission from Semiconductor Electrodes: Experimental.- 9.4. Photoelectron Emission from Solutions into the Vapor Phase. Schematic Aspects of the Process.- 9.5. Principles of the Theory of Photoelectron Emission from Solutions.- 9.6. Photoelectron Emission from Solutions. Basic Experimental Results.- 10. Specific Problems of Photoelectrochemical Phenomena.- 10.1. Currents of Photoelectrochemical Reactions.- 10.2. Currents of the Pulse Warm-Up of the Electrode.- 10.3. Cathodic Generation of Solvated Electrons. Is the Solvated Electron an Intermediate in Cathodic Reactions?.- 10.4. Photoelectrochemical Effects Due to Surface Plasmons.- 10.5. Photoemission into Various Media.- 11. Perspectives of Photoemission Studies.- Appendixes.- References.