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Diamond Electrochemistry
ダイヤモンドの持つ電気化学特性とその応用についての世界初の英文版研究書

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Diamond Electrochemistry

Edited by 藤嶋 昭・栄長 泰明・Tata Narasinga Rao・Donald A Tryk
定価:本体 12,000円+税
発行: 2005年2月
A5判変形上製・604頁 在庫なし

ダイヤモンドは宝石としての魅力だけでなく、最大硬度や大きな屈折率、大きなバンドギャップといった物理的に優れた特性をもっているため、半導体材料をはじめとするさまざまな応用の可能性を秘めている。本書は、ワールドワイドな研究者集団による、ダイヤモンドの電気科学に関する、世界初の研究書。
世界有数の医学・ケミカル系の出版社エルゼビアとの共同出版。

 

The Editors

Professor Akira FujishimaProfessor Akira Fujishima
Professor Fujishima was born in 1942 in Tokyo. He received his Ph. D. in Applied Chemistry at the University of Tokyo in 1971. He taught at Kanagawa University for four years and then moved to the University of Tokyo, where he became a Professor in 1986. In 2003, he retired from this position and took on the position of Chairman at the Kanagawa Academy of Science and Technology. His main interests are in photocatalysis, photoelectrochemistry and diamond electrochemistry.
[Kanagawa Academy of science and Technology, KSP 3-2-1 Sakado, Kawasaki 213-0012, Japan, E-mail: fujishima@kast.or.jp]

Professor Yasuaki EinagaProfessor Yasuaki Einaga
Professor Einaga was born in Niigata Prefecture, Japan in 1971. He received his Ph.D degree in 1999 from The University of Tokyo under the direction of Prof. Akira Fujishima. He joined the Department of Chemistry at Keio University as an Assistant Professor in 2001. In 2003, he was promoted to Associate Professor. His research interests include photo-functional materials science and diamond electrochemistry.
[Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Yokohama 223-8522, Japan, E-mail: einaga@chem.keio.ac.jp]

Dr. Tata Narasinga RaoDr. Tata Narasinga Rao
Dr. Rao was born in India in 1963. He received his Ph.D. degree in 1994 from Banaras Hindu Unversity, India. After working at IIT Madras, he moved to The University of Tokyo as a JSPS Postdoctoral Fellow and became an Assistant Professor in 2001. Presently, he is a senior scientist at the International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI) in Hyderabad, India. His research interests include diamond electrochemistry, nanomaterials synthesis and their applications for environmental remediation.
[International Advanced Research Centre for Powder Metallurgy and New Materials. Balapur PO, Hyderabad 500005, India, E-mail : tatanrao@yahoo.
com]

Dr. Donald A. TrykDr. Donald A. Tryk
Dr. Donald Tryk was born in California (USA) in 1948 and received his Ph. D. in Chemistry from the University of New Mexico in 1980. He was with the Yeager Center for Electrochemical Sciences at Case Western Reserve University in Ohio (USA) before joining Prof. Fujishima’s group in 1995. After two years at Tokyo Metropolitan University, he is now at the University of Puerto Rico. His interests are diamond electrochemistry and electrocatalysis.
[Department of Chemistry, University of Puerto Rico, Rio Piedras Campus, San Juan, Puerto Rico 00931-3346, E-mail : dtryk@goliath.cnnet.clu.edu]

Dr. Ivandini Tribidasari AnggraningrumSpecial Thanks for Contribution
Dr. Ivandini Tribidasari Anggraningrum
Dr. Ivandini was born in Indonesia in 1970 and received her Ph. D. from the University of Tokyo in 2003. She is a lecturer in the Department of Chemistry, Mathematics and Science Faculty, University of Indonesia in Jakarta, Indonesia. Now, she is doing post-doctoral research supported by a JSPS award at the Department of Chemistry, Keio University, Japan. Her interest is in diamond
electrochemistry.

List of Authors

John. C. Angus
Case Western Reserve University, USA
Kazuki Arihara
Central Japan Railway Company, Japan
Orawon Chailapakul
Chulalongkorn University, Thailand
Eun-In Cho
Chungbuk National University, Korea
Christos Comninellis
Swiss Federal Institute of Technology, Switzerland
Ilaria Duo
Swiss Federal Institute of Technology, Switzerland
Sally C. Eaton
Case Western Reserve University, USA
Yasuaki Einaga
Keio University, Japan
Akira Fujishima
Kanagawa Academy of science and Technology, Japan
Tsuneto Furuta
Permelec Electrode Ltd., Japan
Werner Haenni
Centre Suisse d’Electronique et de Microtechnique SA (CSEM), Switzerland
Olivia Herlambang
Canon Inc., Japan
Kensuke Honda
Yamaguchi University, Japan
Tribidasari A. Ivandini
University of Indonesia, Indonesia
Takeshi Kondo
Tokyo University of Science, Japan
Uziel Landau
Case Western Reserve University, USA
Claude Levy-Clement
CNRS, France
Ayyakannu Manivannan
West Virginia University, USA
Beatrice Marselli
Swiss Federal Institute of Technology, Switzerland
Heidi B. Martin
Case Western Reserve University, USA
Hideki Masuda
Tokyo Metropolitan University, Japan
Pierre-Alain Michaud
Swiss Federal Institute of Technology, Switzerland
Yoshinori Nishiki
Permelec Electrode Ltd., Japan
Hideo Notsu
The University of Tokyo, Japan
Soo-Gil Park
Chungbuk National University, Korea
Su-Moon Park
Pohang University of Science & Technology, Korea
Jong-Eun Park
Chungbuk National University, Korea
Gebriele Prosperi
University of Pisa, Italy
Yuri V. Pleskov
Frumkin Institute of Electrochemistry, Russia
Laurent Pupunat
Centre Suisse d’Electronique et de Microtechnique SA (CSEM), Switzerland
Tata N. Rao
International Advanced Research Centre for Powder Metallurgy and New Materials, India
Philippe Rychen
Centre Suisse d’Electronique et de Microtechnique SA (CSEM), Switzerland
Bulusu V. Sarada
The University of Tokyo, Japan
Roberto Massahiro Serikawa
Ebara Research Co. Ltd., Japan
Dongchan Shin
National Institute of Advanced Industrial Science and Technology, Japan
Nicolae Sp?taru
Institute of Physical Chemistry of the Roumanian Academy, Romania
Vembu Suryanarayanan
Utsunomiya University, Japan
Hozumi Tanaka
Permelec Electrode Ltd., Japan
Tetsu Tatsuma
The University of Tokyo, Japan
Chiaki Terashima
GL Sciences Inc., Japan
Donald A. Tryk
University of Puerto Rico, Puerto Rico
Kazuyuki Ueda
Toyota Institute of Technology, Japan
Kohei Uosaki
Hokkaido University, Japan
Nicolaos Vatistas
University of Pisa, Italy
Joseph Wang
New Mexico State University, USA
Ichizo Yagi
Hokkaido University, Japan
Sachio Yoshihara
Utsunomiya University, Japan
Mikiko Yoshimura
Matsushita Electric Industrial Co. Ltd., Japan
Yanrong Zhang
Utsunomiya University, Japan

Contents

1. Historical Survey of Diamond Electrodes
1.1. Introduction
1.2. Origin of Diamond Electrochemistry
1.3. Recent Directions
1.4. Summary

2. Preparation and Characterization of Polycrystalline Chemical Vapor Deposited Boron-doped Diamond Thin Films
2.1. Microwave Plasma-Assisted CVD (MPACVD)
2.2. Hot Filament-Assisted CVD
2.3. Characterization

3. Electrochemical Effects on Diamond Surfaces: Wide Potential Window, Reactivity, Spectroscopy, Doping Levels and Surface Conductivity
3.1. Introduction
3.2. Early studies on Diamond Electrodes
3.3. Properties of Diamond Electrodes
3.4. Semiconducting Diamond Electrodes
3.5. Surface Conductivity of Diamond
3.6 Summary

4. Electrochemistry of Diamond: Semiconductor and Structural Aspects
4.1. Introduction
4.2. Effects of the Semiconductor Nature of Diamond
4.3. Effects of the Crystal Structure
4.4. Conclusions

5. Semiconducting and Metallic Boron-Doped Diamond Electrodes
5.1. Boron Precursors
5.2. Boron Concentration in Diamond Electrodes
5.3. Raman Diffusion Spectroscopy
5.4. Electrochemical Properties
5.5. Conclusions

6. Electrochemical Properties and Application of Diamond Electrodes in Non-Aqueous Electrolytes
6.1. Factors Controlling the Electrochemical Potential Window for Diamond Electrodes in Non-Aqueous Electrolytes
6.2. Electrochemical Characterization of an sp2 – sp3 Composite as a Hybrid Anode for Li-ion Batteries and Super Capacitors

7. Electrochemical Hydrogen and Oxygen Evolution Mechanisms at B-doped Diamond Electrodes Investigated by TOF-ESD Methods 1
7.1. TOF-ESD Method : the “Protoscope”
7.2. Effect of Heating Pretreatment
7.3. Macroscopic Measurements
7.4. Microscopic Measurements
7.5. Hydrogen Evolution Mechanism at the B-doped Diamond Electrode
7.6. Effect of Oxygen Evolution at the B-doped Diamond Electrode on Protoscope Images

8. Single-Crystal Homoepitaxial Diamond Electrodes
8.1. Preparation of Homoepitaxial Diamond Electrodes
8.2. Electrochemical Properties of Homoepitaxial Diamond Electrodes
8.3. Applications in Electroanalysis
8.4. Surface Modification of Homoepitaxial Diamond Electrodes
8.5. Nanolithographic Modification of Diamond with AFM Techniques
8.6. Conclusions

9. Chemical, Photochemical and Electrochemical Modification of Diamond
9.1. Introduction
9.2. Chemical Modification Methods
9.3. Photochemical Modification Methods
9.4. Electrochemical Modification Methods
9.5. Combined Methods: Electrochemical/Chemical methods
9.6. Metal and Metal Oxides on Diamond Surfaces
9.7. Conclusions

10. Characterization of Oxygenated Diamond Electrodes
10.1. Surface Oxidation of Diamond
10.2. Contact Angle of Water Droplets
10.3. Electrochemical Character of Oxidized Diamond Electrodes
10.4. Electrochemical Responses to Several Redox Systems
10.5. XPS Spectra of Oxidized Diamond Electrodes
10.6. Carboxyl Groups on the Diamond Surface
10.7. Carbonyl Groups on the Diamond Surface
10.8. Hydroxyl Groups on the Diamond Surface
10.9. Correlation between Redox Behavior and Surface Groups
10.10. Applications of Oxidized Diamond Electrodes

11. Diamond Electrodes with Functional Structures and Surfaces
11.1. Boron-Doped Diamond Microdisk Array Electrodes
11.2. Ion-Implanted Boron-Doped Diamond Electrodes
11.3. Boron-Doped Diamond Electrodes with Smoothed Surfaces
11.4. Conclusions

12. Electroanalytical Applications of Highly Boron-Doped Diamond Electrode
12.1. Introduction
12.2. Electroanalysis with As-Deposited Boron-Doped Diamond Electrodes
12.3. Electroanalysis at Oxidized Diamond Electrodes
12.4. Summary

13. Anodic Voltammetry at Conductive Diamond Electrodes and Its Analytical Applications
13.1. Wide Potential Window in Aqueous Solutions
13.2. Inertness to Adsorption
13.3. High Chemical and Electrochemical Stability

14. Diamond Electrochemical Detector in Capillary Electrophoresis
14.1. Introduction
14.2. Preparation of Capillary Electrophoresis
14.3. Applications
14.4. Conclusions

15. Determination and Electrooxidation of Sulfur-Containing Compounds at Boron-Doped Diamond Electrodes1
15.1. Introduction
15.2. Detection of Sulfur-Containing Compounds
15.3. Detection of Sulfur-Containing Drugs

16. Boron-Doped Diamond Electrodes for the Analysis of Trace Metals
16.1. Introduction
16.2. Mercury-Film Assisted Analysis
16.3. Mercury-Free Metal Detection
16.4. Special Techniques
16.5. Conclusions and Future Prospects

17. Industrial Applications of Boron-Doped Diamond Electrodes: Detection of Sodium Thiosulfate, Naproxen and Nickel Ions and Electrocatalysis of Oxygen Reduction
17.1. Electroanalysis of Sodium Thiosulfate
17.2. Electroanalysis of Naproxen
17.3. Electrochemical Detection of Nickel Ions in Solution
17.4. Electrocatalysis of Oxygen

18. Diamond Microelectrodes
18.1. Introduction
18.2. Preparation of Diamond Microelectrodes
18.3. Electrochemical Behavior
18.4. Electroanalytical Applications of Diamond Microelectrodes
18.5. Summary

19. Electrochemistry at Nanostructured Diamond Electrodes : Characterization and Applications
19.1. Introduction
19.2. Fabrication of Nanostructured Diamond 414
19.3. Impedance Characteristics of the Nanoporous Honeycomb Diamond and Application as an Electrical Double?Layer Capacitor
19.4. Electrochemical Properties of Pt?Modified Nanohoneycomb Diamond and Applications as a Size Selective Sensor Materials

20. Application of Synthetic Boron-Doped Diamond Electrodes in Electrooxidation Processes
20.1. Introduction
20.2. Application of BDD in Electrosynthesis
20.3. Application of BDD in the Electrochemical Combustion of Organic Pollutants

21. Oxidant Production on BDD Anodes and Advanced Oxidation Processes
21.1. Mass Transfer Limitation in the Direct Electrochemical Wastewater Treatment Process
21.2. Peroxide Production on BDD Anodes Followed by Advanced Oxidation Processes in a Separate Chemical Reactor
21.3. Homogeneous and Heterogeneous Advanced Oxidation Processes
21.4. Peroxodisulfate/Heat Advanced Oxidation Processes
21.5. The Peroxodisulfate/Heat Homogeneous Process
21.6. The Combined Heterogeneous-Homogeneous Peroxodisulfate/Heat Process
21.7. Conclusions

22. Ozone Generation with Boron-Doped Diamond Electrodes and Its Applications 5
22.1. Introduction
22.2. Ozone Generation with Diamond Electrodes: Experimental
22.3. Factors Influencing Ozone Generation
22.4. Durability Testing
22.5. Applications of Ozone
22.6. Conclusions

23. Application of Diamond Electrodes for Water Disinfection
23.1. Oxidant Production Capacity of BDD Electrodes
23.2. Legionella Inactivation with BDD Electrodes
23.3. Concluding Remarks

24. Direct Ozone-Water Generation by Electrolysis: Novel Application of Self-Standing Diamond Electrodes
24.1. Introduction
24.2. New Forms of Diamond Electrodes for Ozone Generation
24.3. Direct Ozone-Water Generation with Self-standing Perforated Diamond Electrodes
24.4. Conclusions and Future Development

25. Fundamental and Applied Aspects of Diamond Electrodes
25.1. Introduction
25.2. Wide Working Potential Window
25.3. Low Double Layer Capacitance
25.4. Inertness to Adsorption
25.5. Dimensional Stability
25.6. Applications

Preface

It has been nearly ten years since we began to build an international consortium in the area of diamond electrochemistry, with our First International Mini-Symposium, held in Tokyo in 1997. Since that time, we have tried to keep this tradition going. In addition, there have been International Symposia on Diamond Materials every two years, held under the auspices of the Electrochemical Society, with a strong complement of presentations in the area of electrochemical applications of conductive diamond. These symposia, together with others, such as the European Conferences on Diamond and Diamond-Like Materials and the International Conferences on New Diamond Science and Technology, held in the Eastern Hemisphere, have kept this field growing at a rapid rate. Almost every aspect of electrochemistry has been impacted by the diamond electrode, from electroanalysis to electrolysis.
Recently also, the field has started to mature, with the development of many practical applications of diamond electrodes. Some of these are being commercialized at present. Two examples are the diamond electrochemical detector for liquid chromatography and the large-scale diamond electrode for industrial wastewater treatment.
For the present volume, we have invited representatives from nearly every group in the world that has been active in the field, and we are very pleased that many of these groups have responded with chapters devoted to both their own work as well as that of others. Certainly we realize that it is virtually impossible to capture everything that is going on in any given field at a particular time, but our group of authors has tried hard to accomplish the impossible.
In Chapter 1, Rao, et al., have provided a historical introduction to the area, which got its start in 1983 in Japan in a publication by Iwaki et al. In Chapter 2, Ivandini, et al., provide further historical perspective and introduce the basics of the preparation and characterization of chemical vapor-deposited (CVD) diamond films. In Chapter 3, Martin, et al., discuss several fundamental aspects of diamond electrochemistry, including the large working potential range (“wide potential window”), aspects of the reactivity, the optical transparency, semiconductor aspects, and the surface conductivity phenomenon. In Chapter 4, Pleskov gives a full account of the semiconductor aspects of diamond electrochemistry. In Chapter 5, Levy-Clement focuses on the role of the boron doping level in determining the electrochemical properties, together with Raman spectroscopy as a useful diagnostic tool in estimating the effective doping level. In Chapter 6, Yoshimura et al. examine the factors that determine the potential working range for various non-aqueous solvent/electrolyte systems, including theoretical molecular orbital calculations. In Chapter 7, Yagi, et al., examine the use of a novel technique, time-of-flight electron-stimulated desorption, as a means of understanding the interactions of the diamond surface with hydrogen, the most important of the surface terminations. In Chapter 8, Kondo, et al., examine the electrochemistry of single-crystal-like homoepitaxial diamond films, particularly as nearly ideal electrodes for electroanalytical applications. In Chapter 9, Tryk, et al., review the various techniques available for the chemical modification of the diamond surface, including ways of attaching DNA strands. In Chapter 10, Notsu, et al., focus on the oxidized diamond surface, which is the most common form of chemically modified diamond surface. In Chapter 11, Einaga, et al., present several different ways of producing functional diamond surfaces, including diamond microelectrode arrays, diamond surfaces ion-implanted with metals to impart catalytic activity, and ultrasmooth diamond surfaces produced by the glow discharge technique. In Chapter 13, Sp?taru, et al., focus on the advantages of the diamond electrode for the oxidative determination of various types of biologically active compounds. In Chapter 14, Shin, et al., discuss the use of the boron-diamond electrode as a detector for capillary zone eletrophoresis, which is quickly becoming a powerful technique for the detection of a number of different types of compound mixtures, for example, explosives, as well as biologically active compounds such as neurotransmitters. In Chapter 15, Orawon, et al., discuss the use of diamond electrodes for the determination of the biologically important sulfur-containing compounds. In Chapter 16, Manivannan, et al., examine the diamond electrode for use in the detection of trace concentrations of toxic metals. In Chapter 17, Suryanarayanan, et al., examine several diverse examples of analytical applications of boron-doped diamond electrodes for industrially important chemicals. In Chapter 18, Olivia, et al., present the topic of boron-doped diamond microelectrodes, which are highly interesting and analytically useful, because they combine the advantages of diamond with those of the microelectrode, including efficient mass transport. In Chapter 19, Honda and Fujishima discuss the highly interesting nanotextured diamond surfaces, along with possible applications of such electrodes. In Chapter 20, Comninellis, et al., discuss the use of hydroxyl radicals generated at the diamond surface to carry out various types of oxidation reactions, including electrosynthetic processes, and the electrochemical “combustion” of organic compounds. In Chapter 21, Vatistas, et al., examine a highly useful approach to the use of diamond for wastewater treatment, i.e., involving the electrogeneration of hydroxyl radicals, followed by the reaction of these radicals with inorganic ions such as sulfate to produce active oxidants, circumventing the mass transport problems associated with the direct reaction of hydroxyl radicals with pollutants. In Chapter 22, Cho, et al., focus on the use of diamond electrodes for the electrogeneration of ozone, which is an important oxidant and potential replacement for chlorine. In Chapter 23, Furuta, et al., provide a very interesting account of the practical use of diamond electrodes in ordinary tap water to produce oxidants that are capable of destroying the bacteria that cause Legionnaires’ Disease. In Chapter 24, Arihara and Fujishima provide an additional account of how diamond electrodes, specifically, free-standing ones, can be used successfully to produce ozone-water, which is an environmentally friendly decolorizing and antibacterial agent. Finally, in Chapter 25, Rao, et al., provide a summary and perspective on the fundamental and applied aspects of diamond electrodes.
Lastly, we would very much like to acknowledge the great contribution of Dr. Ivandini Tribidasari in assembling this volume, which could not have been completed otherwise.

Akira Fujishima

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