Electrochemistry at Metal and Semiconductor Electrodes

by Sato

• ISBN13: 9780444828064
• ISBN10: 0444828060
• Format: Hardcover
• Copyright: 1998-10-09
• Publisher: Elsevier Science

Summary

Electrochemisty at Metal and Semiconductor Electrodes covers the structure of the electrical double layer and charge transfer reactions across the electrode/electrolyte interface. The purpose of the book is to integrate modern electrochemistry and semiconductor physics, thereby, providing a quantitative basis for understanding electrochemistry at metal and semiconductor electrodes.Electrons and ions are the principal particles which play the main role in electrochemistry. This text, therefore, emphasizes the energy level concepts of electrons and ions rather than the phenomenological thermodynamic and kinetic concepts on which most of the classical electrochemistry texts are based. This rationalization of the phenomenological concepts in terms of the physics of semiconductors should enable readers to develop more atomistic and quantitative insights into processes that occur at electrodes.The book incorporates many traditional disciplines of science and engineering such as interfacial chemistry, biochemistry, enzyme chemistry, membrane chemistry, metallurgy, modification of solid interfaces, and materials' corrosion. The text is intended to serve as an introduction for the study of advanced electrochemistry at electrodes and is aimed towards graduates and senior undergraduates studying materials and interfacial chemistry or those beginning research work in the field of electrochemistry.

Table of Contents

CHAPTER 1 THE ENERGY LEVEL OF PARTICLES	1	(14)
1.1 Particles and Particle Ensembles	1	(3)
1.2 Chemical Potential and Electrochemical Potential	4	(1)
1.3 Electrochemical Potential of Electrons	5	(3)
1.4 The Reference Level of Particle Energy	8	(1)
1.5 Electrostatic Potential of Condensed Phases	9	(2)
1.6 Energy Levels of Charged Particles in Condensed Phases	11	(2)
References	13	(2)
CHAPTER 2 THE ENERGY LEVEL OF ELECTRONS	15	(46)
2.1 Energy Levels of Electrons in Condensed Phases	15	(4)
2.2 Electrons in Metals	19	(5)
2.2.1 Energy band and the Fermi level	19	(2)
2.2.2 The real potential and the chemical potential of electrons in metals	21	(3)
2.3 Electron Energy Bands of Semiconductors	24	(3)
2.4 Electrons and Holes in Semiconductors	27	(5)
2.4.1 Intrinsic semiconductors	27	(2)
2.4.2 n-type and p-type semiconductors	29	(3)
2.5 Energy Levels of Electrons in Semiconductors	32	(3)
2.6 Metal Oxides	35	(4)
2.6.1 Formation of electron energy bands	35	(3)
2.6.2 Localized electron levels	38	(1)
2.7 The Surface of Semiconductors	39	(5)
2.7.1 The surface state	39	(3)
2.7.2 The space charge layer	42	(2)
2.7.3 Surface degeneracy (Quasi-metallization of surfaces)	44	(1)
2.8 Amorphous Semiconductors	44	(1)
2.9 Electron Energy Bands of Liquid Water	45	(2)
2.10 Redox Electrons in Aqueous Solution	47	(8)
2.10.1 Electron levels of gaseous redox particles	47	(1)
2.10.2 Electron levels of hydrated redox particles	48	(3)
2.10.3 Fluctuation of electron energy levels	51	(2)
2.10.4 The Fermi level of hydrated redox electrons	53	(2)
2.11 The Electron Level of Normal Hydrogen Electrode	55	(3)
References	58	(3)
CHAPTER 3 THE ENERGY LEVEL OF IONS	61	(26)
3.1 Ionic Dissociation of Gaseous Molecules	61	(2)
3.2 Metal Ion Levels in Solid Metals	63	(4)
3.2.1 The unitary energy level of surface metal ions	63	(2)
3.2.2 Metal ion levels at the surface and in the interior	65	(2)
3.3 Ion Levels of Covalent Semiconductors	67	(4)
3.3.1 The unitary level of surface ions	67	(2)
3.3.2 Ion levels at the surface and in the interior	69	(2)
3.4 Ion Levels of Compound Semiconductors	71	(5)
3.4.1 The unitary level of surface ions	71	(3)
3.4.2 Ion levels at the surface and in the interior	74	(2)
3.5 Ion Levels in Aqueous Solution	76	(9)
3.5.1 Levels of hydrated ions	76	(2)
3.5.2 Proton levels in aqueous solution	78	(7)
3.6 Thermodynamic Reference Level for Ions	85	(1)
References	86	(1)
CHAPTER 4 ELECTRODE POTENTIAL	87	(32)
4.1 Electrode	87	(3)
4.1.1 Electrode	87	(1)
4.1.2 Anode and cathode	88	(1)
4.1.3 Electronic electrode and ionic electrode	88	(1)
4.1.4 Polarizable and nonpolarizable electrodes	89	(1)
4.2 The Interface of Two Condensed Phases	90	(6)
4.2.1 Potential difference between two contacting phases	90	(3)
4.2.2 The interface of zero charge	93	(1)
4.2.3 Interfaces in charge transfer equilibrium	94	(2)
4.3 Electrode Potential	96	(7)
4.3.1 Electrode potential defined by electron energy levels	96	(5)
4.3.2 Electrode potential and ion energy levels in electrodes	101	(2)
4.4 Electrode Potential in Charge Transfer Equilibrium	103	(7)
4.4.1 Electrode potential in electron transfer equilibrium	103	(2)
4.4.2 Electrode potential in ion transfer equilibrium	105	(2)
4.4.3 Potential of film-covered ionic electrodes in equilibrium	107	(1)
4.4.4 Potential of gas electrodes in equilibrium	108	(2)
4.5 Measurement of Electrode Potentials	110	(2)
4.6 Potential of the Emersed Electrode	112	(5)
4.6.1 Potential of emersed electrodes in vacuum	113	(1)
4.6.2 Potential of emersed electrodes in inactive gas	114	(3)
References	117	(2)
CHAPTER 5 ELECTRIC DOUBLE LAYER AT ELECTRODE INTERFACES	119	(82)
5.1 Solid Surface and Adsorption	119	(8)
5.1.1 Clean surface of solids	119	(2)
5.1.2 Adsorption	121	(1)
5.1.3 Electron level of adsorbed particles	122	(5)
5.2 Electric Double Layer at Solid/Aqueous Solution Interfaces	127	(5)
5.2.1 Electric double layer model	127	(2)
5.2.2 Diffuse charge layer (Space charge layer)	129	(3)
5.3 The Potential of Zero Charge on Metal Electrodes	132	(6)
5.3.1 Classical model of the compact double layer at interfaces	132	(3)
5.3.2 The potential of zero charge	135	(3)
5.4 Thermodynamics of Adsorption on Metal Electrodes	138	(5)
5.4.1 Gibbs' adsorption equation	138	(1)
5.4.2 Ion adsorption on mercury electrodes	139	(3)
5.4.3 Contact adsorption of ions	142	(1)
5.5 Electric Double Layer at Metal Electrodes	143	(8)
5.5.1 Interfacial electric capacity (Electrode capacity)	143	(1)
5.5.2 The effective image plane on metal surfaces	144	(2)
5.5.3 The closest approach of water molecules to electrode interfaces	146	(2)
5.5.4 Electric capacity of the compact layer	148	(2)
5.5.5 Potential difference across the compact double layer	150	(1)
5.6 Contact Adsorption and Electric Double Layer	151	(7)
5.6.1 Contact adsorption and work function	151	(2)
5.6.2 Interfacial dipole moment induced by contact adsorption	153	(2)
5.6.3 Interfacial potential difference affected by contact adsorption	155	(3)
5.7 Particle Adsorption on Metal Electrodes	158	(10)
5.7.1 Adsorption of water molecules	158	(3)
5.7.2 Coadsorption of water molecules and third-particles	161	(1)
5.7.3 Surface lattice transformation due to contact adsorption	162	(3)
5.7.4 Electron energy levels of adsorbed particles	165	(3)
5.8 Electric Double Layer at Semiconductor Electrodes	168	(3)
5.8.1 Electric double layer model	168	(1)
5.8.2 Potential distribution across the electrode interface	169	(2)
5.9 Band Edge Level Pinning and Fermi Level Pinning	171	(3)
5.10 The Space Charge Layer of Semiconductor Electrodes	174	(7)
5.10.1 Space charge layers	174	(2)
5.10.2 Differential electric capacity of space charge layers	176	(5)
5.10.3 Schottky barrier	181	(1)
5.11 The Compact Layer at Semiconductor Electrodes	181	(7)
5.11.1 Hydroxylation of electrode interfaces	181	(3)
5.11.2 The compact layer	184	(3)
5.11.3 Differential electric capacity of electrode interfaces	187	(1)
5.12 The Surface State of Semiconductor Electrodes	188	(4)
5.12.1 Surface states	188	(2)
5.12.2 Differential electric capacity of surface states	190	(2)
5.13 The Flat Band Potential of Semiconductor Electrodes	192	(4)
5.13.1 Flat band potential	192	(3)
5.13.2 Band edge potential	195	(1)
References	196	(5)
CHAPTER 6 ELECTROCHEMICAL CELLS	201	(12)
6.1 Electrochemical Cells	201	(3)
6.2 Electromotive Force of Electrochemical Cells	204	(2)
6.3 Equilibrium Potential of Electrode Reactions	206	(4)
6.3.1 Equilibrium potential of electron transfer reactions	206	(2)
6.3.2 Equilibrium potential of ion transfer reactions	208	(2)
6.4 Electrochemical Reference Level for Hydrated Ions	210	(1)
References	211	(2)
CHAPTER 7 ELECTRODE REACTIONS	213	(22)
7.1 Electrode Reactions	213	(3)
7.1.1 Electron transfer and ion transfer reactions	213	(1)
7.1.2 Cathodic and anodic reactions	213	(1)
7.1.3 Electron transfer of hydrated particles and adsorbed particles	214	(2)
7.2 Reaction Rate	216	(4)
7.2.1 Forward and backward reaction affinities	216	(1)
7.2.2 Reaction rate	217	(1)
7.2.3 Polarization curve of electrode reactions	218	(2)
7.3 Reaction Mechanism	220	(6)
7.3.1 The stoichiometric number of reactions	220	(1)
7.3.2 The activation energy	221	(2)
7.3.3 Quantum tunneling and activated flow of particles	223	(2)
7.3.4 The reaction order	225	(1)
7.4 Rate-Determining Steps of Reactions	226	(7)
7.4.1 Reaction of elementary steps in series	226	(2)
7.4.2 Reaction rate determined by a single step	228	(1)
7.4.3 Reaction rate determined by multiple steps	229	(1)
7.4.4 Affinity distributed to elementary steps	230	(2)
7.4.5 Rate of multistep reactions	232	(1)
References	233	(2)
CHAPTER 8 ELECTRODE REACTIONS IN ELECTRON TRANSFER	235	(54)
8.1 Electron Transfer at Metal Electrodes	235	(14)
8.1.1 Kinetics of electron transfer	235	(3)
8.1.2 The state density of redox electrons	238	(2)
8.1.3 Exchange reaction current at the equilibrium potential	240	(2)
8.1.4 Reaction current under polarization	242	(3)
8.1.5 Diffusion and reaction rate	245	(4)
8.2 Electron Transfer at Semiconductor Electrodes	249	(9)
8.2.1 Semiconductor electrodes compared with metal electrodes	249	(1)
8.2.2 The conduction band and the valence band mechanisms	250	(2)
8.2.3 Electron state density in redox electrode reactions	252	(2)
8.2.4 Exchange reaction current at the equilibrium potential	254	(4)
8.3 Reaction Current at Semiconductor Electrodes	258	(16)
8.3.1 Reaction current under polarization	258	(4)
8.3.2 Reaction current versus potential curve	262	(4)
8.3.3 The transport overvoltage of minority carriers	266	(1)
8.3.4 Recombination of minority carriers	267	(1)
8.3.5 Polarization curves of redox electron transfers	268	(2)
8.3.6 Redox Fermi level and band edge level	270	(2)
8.3.7 Electron transfer via the surface state	272	(2)
8.3.8 Electron tunneling through the space charge layer	274	(1)
8.4 Complexation and Adsorption in Electron Transfer Reactions	274	(7)
8.4.1 Complexation shifts the redox electron level	275	(3)
8.4.2 Contact adsorption shifts the redox electron level	278	(3)
8.5 Electron Transfer at Film-Covered Metal Electrodes	281	(6)
8.5.1 Electron transfer between the electrode metal and the redox particles	282	(2)
8.5.2 Electron transfer between the film and the redox particles	284	(2)
8.5.3 Polarization curves observed	286	(1)
References	287	(2)
CHAPTER 9 ELECTRODE REACTIONS IN ION TRANSFER	289	(36)
9.1 Metal Ion Transfer at Metal Electrodes	289	(9)
9.1.1 Metal ion transfer in a single elemental step	289	(5)
9.1.2 Metal ion transfer in a series of two elemental steps	294	(4)
9.2 Ion Transfer at Semiconductor Electrodes	298	(16)
9.2.1 Surface atom ionization of covalent semiconductor electrodes	298	(4)
9.2.2 Dissolution of covalent semiconductors	302	(3)
9.2.3 Dissolution of ionic semiconductors	305	(4)
9.2.4 Oxidative and reductive dissolution of ionic semiconductors	309	(5)
9.3 Ion Adsorption on Metal Electrodes	314	(3)
9.3.1 Ion adsorption equilibrium	314	(1)
9.3.2 Electron levels of adsorbed ions	315	(2)
9.4 Ion Adsorption on Semiconductor Electrodes	317	(5)
9.4.1 Ion adsorption equilibrium	317	(1)
9.4.2 Electron levels of adsorbed ions	317	(2)
9.4.3 Proton levels on electrode surfaces	319	(3)
References	322	(3)
CHAPTER 10 SEMICONDUCTOR PHOTOELECTRODES	325	(48)
10.1 Quasi-Fermi Level of Excited Electrons and Holes	325	(5)
10.1.1 Quasi-Fermi level	325	(3)
10.1.2 Quasi-Fermi levels and electrode reactions	328	(2)
10.2 Photopotential	330	(4)
10.3 Photoexcited Electrode Reactions	334	(13)
10.3.1 Photoexcited electrode reaction current (Photocurrent)	334	(4)
10.3.2 The range of electrode potential for photoelectrode reactions	338	(6)
10.3.3 The flat band potential of photoexcited electrodes	344	(3)
10.4 The Rate of Photoelectrode Reactions	347	(10)
10.4.1 Anodic transfer reactions of photoexcited holes	347	(2)
10.4.2 Generation and transport of holes	349	(1)
10.4.3 Interfacial overvoltage of hole transfer	350	(2)
10.4.4 Recombination of photoexcited holes in anodic reactions	352	(2)
10.4.5 Cathodic hole injection reactions	354	(3)
10.5 Photoelectrochemical Cells	357	(1)
10.6 Photoelectrolytic Cells	357	(10)
10.6.1 Photoelectrolytic cells of metal and semiconductor electrodes	357	(7)
10.6.2 Photoelectrolytic cells of two semiconductor electrodes	364	(3)
10.7 Photovoltaic Cells	367	(4)
References	371	(2)
CHAPTER 11 MIXED ELECTRODES	373	(18)
11.1 The Single Electrode and The Mixed Electrode	373	(2)
11.2 Catalytic Reactions on Mixed Electrodes	375	(2)
11.3 Mixed Electrode Potential	377	(4)
11.4 Passivation of Metal Electrodes	381	(8)
11.4.1 Polarization curve of anodic metal dissolution	381	(2)
11.4.2 Metal dissolution in the passive and transpassive states	383	(4)
11.4.3 Spontaneous passivation of metal electrodes	387	(2)
References	389	(2)
LIST OF SYMBOLS	391	(6)
INDEX	397