PREFACE ....................................................... xix
PREFACE TO THE WILEY SERIES ON ELECTROCATALYSIS AND
ELECTROCHEMISTRY ............................................ xxiii
CONTRIBUTORS .................................................. xxv
PART I SYNTHESIS OF DIAMOND FILMS .............................. 1
1 Electrochemistry on Diamond: History and Current Status ...... 3
John C. Angus
1.1 Enabling Technologies ................................... 3
1.1.1 Chemical Vapor Deposition of Diamond ............. 3
1.1.2 Doping of Diamond ................................ 4
1.1.3 Surface Characterization of Diamond .............. 5
1.2 First Studies of the Electrochemistry on Diamond ........ 5
1.2.1 From 1987 to 1996 ................................ 5
1.2.2 From 1996 to Present ............................. 6
1.3 Development of Electrochemical Applications of Diamond .. 8
1.3.1 Surface Functionalization ........................ 8
1.3.2 Destruction of Wastes ............................ 9
1.3.3 Sensors and Electroanalysis ...................... 9
1.4 Other Directions ....................................... 10
1.4.1 Biolectronic Applications ....................... 10
1.4.2 Anomalous Surface Conductivity of Diamond ....... 11
Conclusions ................................................. 13
References .................................................. 13
2 Synthesis of Diamond Films
Vadali V.S.S. Srikanth and Xin Jiang
2.1 Introduction ........................................... 21
2.2 Diamond Film CVD Techniques ............................ 23
2.2.1 History ......................................... 23
2.2.2 Thermal Decomposition Techniques ................ 25
2.2.2.1 Hot Filament Chemical Vapor
Deposition (HFCVD) ..................... 25
2.2.2.2 Oxy-Acetylene Torch Method ............. 25
2.2.3 Plasma-Aided Deposition Techniques .............. 26
2.2.3.1 Microwave Plasma-Enhanced CVD
(MWCVD) ................................ 26
2.2.3.2 DC Plasma CVD .......................... 27
2.2.3.3 RF Plasma CVD .......................... 28
2.2.3.4 Electron Cyclotron Resonance
Microwave Plasma-Assisted CVD .......... 28
2.3 Diamond Nucleation and Growth .......................... 28
2.3.1 Nucleation ...................................... 28
2.3.1.1 Definition and Types ................... 28
2.3.1.2 Methods ................................ 30
2.3.2 Growth .......................................... 32
2.3.3 Role of Hydrogen and Oxygen ..................... 39
2.4 Diamond Epitaxy ........................................ 40
2.5 Nanodiamond Thin Films ................................. 45
2.6 Diamond Nanocomposite Films ............................ 46
2.7 Conclusions ............................................ 48
References .................................................. 48
3 Types of Conducting Diamond Materials and Their Properties .. 57
Marco A. Quiroz and Erick R. Bandala
3.1 introduction ........................................... 57
3.2 Conducting Diamond Materials (CDMs) .................... 62
3.3 CDM Preparation Procedures ............................. 63
3.4 CDM Doping Materials ................................... 63
3.4.1 Characteristics of Boron-Doped CDMs ............. 63
3.4.2 Electrochemical Properties ...................... 64
3.4.3 Photoelectrochemical Properties ................. 66
3.4.4 Optical Spectroscopy Properties ................. 67
3.4.5 Photo- and Cathodoluminescence Properties ....... 68
3.4.6 Electrical Conductivity and Superconductivity
Properties ...................................... 69
3.5 Non-Boron-Doped CDMs ................................... 69
3.6 Conclusions ............................................ 71
References .................................................. 71
PART II ELECTROCHEMISTRY OF DIAMOND FILMS ..................... 77
4 Electrochemistry of Diamond ................................. 79
Yuri Pleskov
4.1 Introduction ........................................... 79
4.2 Principal Electrochemical Properties of Diamond ........ 80
4.3 The Effect of Semiconductor Nature of Diamond on its
Electrochemical Behavior ............................... 83
4.4 The Effect of Crystal Structure on the
Electrochemical Behavior of Diamond .................... 92
4.4.1 The Effect of Crystallographic Orientation of
Crystal Faces ................................... 92
4.4.2 The Effect of Surface Morphology ................ 95
4.4.3 The Effect of the Diamond Grain Size (or the
Film Thickness, or the sp2-Carbon Impurity) ..... 98
4.5 Diamond-Based Nanostructures as Electrode Materials:
Vacuum-Annealed Undoped Polycrystalline Diamond ....... 102
4.6 Conclusions ........................................... 106
4.7 Acknowledgments ....................................... 106
References ................................................. 106
5 Applications of Polycrystalline and Modified Functional
Diamond Electrodes ......................................... 109
Yasuaki Einaga and Akira Fujishima
5.1 Introduction .......................................... 109
5.2 Preparation of BDD Electrodes ......................... 110
5.3 Electrochemical Properties of BDD as Electrode
Materials ............................................. 111
5.4 Applications in Electrochemical Analysis Using
Polycrystalline BDD electrodes ........................ 111
5.4.1 Detection of Free Chlorine ..................... 111
5.4.2 Detection of Oxalic Acid ....................... 113
5.4.3 Proteins (Including Cancer Markers) ............ 113
5.5 Modified Functional BDD Electrodes .................... 116
5.5.1 Production of High-Concentration Ozone-Water
Using Free-Standing Perforated Diamond ......... 116
5.5.2 Modified Functional BDD Electrodes for
Electrochemical Analysis ....................... 119
5.5.2.1 Ion-Implanted BDD Electrodes .......... 119
5.5.2.2 Selective Detection ofAs(III) and
As(V) by Stripping Voltammetry ........ 124
5.5.2.3 In vivo Dopamine Detection by BDD
Microelectrodes ....................... 125
5.5.2.4 BDD Nanograss Array (Whisker BDD) ..... 126
5.6 Conclusions ........................................... 130
5.7 Acknowledgments ....................................... 130
References ................................................. 131
6 Diamond Ultramicroelectrodes and Nanostructured
Electrodes ................................................. 133
Katherine В. Holt
6.1 Introduction .......................................... 133
6.2 Ultramicroelectrodes: Definition and Electrochemical
Characteristics ....................................... 134
6.3 Boron-Doped Diamond UMEs .............................. 136
6.3.1 Substrate Preparation and Growth of Diamond
Films .......................................... 136
6.3.2 Insulation Methods and Control of Exposed
Electrode Geometry ............................. 140
6.3.3 Electrochemical Performance and Applications ... 142
6.4 Boron-Doped Diamond UME Arrays ........................ 143
6.4.1 Fabrication of BDD UME Arrays .................. 144
6.4.2 Electrochemical Performance and Applications ... 146
6.5 Nanostructured BDD Electrodes ......................... 147
6.5.1 Random Array BDD Nanodisk Electrodes ........... 147
6.5.2 Fabrication of Nanostructured BDD Arrays ....... 148
6.5.3 Electrochemical Performance and Applications
of Nanostructured BDD Electrodes ............... 149
6.6 Conclusions and Future Directions ..................... 150
References ................................................. 151
PART III ELECTROANALYTICAL APPLICATIONS ....................... 153
7 Electroanalytical Applications of Diamond Films ............ 155
Weena Siangproh, Amara Apilux, Pimkwan Chantarateepra,
and Orawon Chailapakul
7.1 Introduction .......................................... 155
7.2 Pharmaceutical Compounds .............................. 156
7.3 Biomolecules or Biological Compounds .................. 159
7.4 Pollutant Compounds ................................... 162
7.5 Heavy Metals .......................................... 165
7.6 Food and Dietary Contaminants ......................... 166
7.7 Miscellaneous ......................................... 168
7.8 Conclusions ........................................... 170
7.9 Acknowledgments ....................................... 178
References ................................................. 178
8 Cathodic Pretreatment of Boron-Doped Diamond Electrodes
and Their Use in Electroanalysis ........................... 181
Leonardo S. Andrade, Giancarlo R. Salazar-Banda, Romeu
C. Rocha-Filho, and Orlando Fatibello-Filho
8.1 Introduction .......................................... 181
8.2 Cathodic Pretreatment of Conductive Diamond Films ..... 182
8.3 Electroanalytical Applications ........................ 192
8.3.1 General Aspects ................................ 192
8.3.2 Determination of Pesticides in Environmental
Samples ........................................ 193
8.3.2.1 Carbaryl .............................. 193
8.3.2.2 4-Nitrophenol ......................... 193
8.3.2.3 Chlorophenols ......................... 196
8.3.3 Determination of Substances in Food Samples .... 198
8.3.3.1 Aspartame ............................. 198
8.3.3.2 Sodium Cyclamate ...................... 199
8.3.3.3 Aspartame and Sodium Cyclamate ........ 200
8.3.3.4 Total Phenols ......................... 201
8.3.4 Determination of Substances in Pharmaceutical
Samples ........................................ 201
8.3.4.1 Sulfamethoxazole and Trimethoprim ..... 201
8.3.4.2 Sulfamethoxazole and Sulfadiazine ..... 205
8.3.4.3 Acetylsalicylic Acid .................. 205
8.3.4.4 Paracetamol and Caffeine .............. 206
8.3.4.5 Sildenafil Citrate (Viagra®) .......... 206
8.3.4.6 Lidocaine ............................. 207
8.4 Gold Deposition and Stripping ......................... 209
8.5 Conclusions ........................................... 209
References ................................................. 210
PART IV INDUSTRIAL APPLICATIONS ............................... 213
9 Use of Boron-Doped Diamond Electrode in Electrochemical
Generation and Applications of Ferrate ..................... 215
Virender K. Sharma, Enric Brillas, Ignasi Sirés, and
Karel Bouzek
9.1 Introduction .......................................... 215
9.2 Electrochemical Generation of the Ferrate Ion with
Iron Anodes ........................................... 217
9.3 Electrochemical Generation of the Ferrate Ion with
Inert Anodes .......................................... 222
9.4 Electrochemical Generation of the Ferrate Ion with
Boron-Doped Diamond Anode ............................. 223
9.4.1 Acidic Medium .................................. 223
9.4.2 Alkaline Medium ................................ 225
9.5 Applications .......................................... 228
9.5.1 Common Inert Anodes ............................ 228
9.5.2 Iron Anodes .................................... 229
9.5.3 BDD Anode ...................................... 230
9.6 Conclusions ........................................... 233
9.7 Acknowlegments ........................................ 233
References ................................................. 233
10 Electrochemical Oxidation of Organic Compounds Induced by
Electro-Generated Free Hydroxyl Radicals on BDD
Electrodes ................................................. 237
Agnieszka Kapalka, Helmut Baltruschat, and Christos
Comninellis
10.1 Introduction .......................................... 237
10.2 Influence of Anode Material on the Reactivity of
Electrolytic Hydroxyl Radicals ........................ 238
10.3 Electro-Generation and Detection of Quasi-Free
Hydroxyl Radicals on BDD Electrode .................... 240
10.3.1 Hydroxyl Radicals Spin Trapping ................ 240
10.3.2 Trapping by Salicylic Acid ..................... 240
10.3.3 Competitive Reactions .......................... 242
10.3.4 Formation of Hydrogen Peroxide ................. 242
10.4 Concentration Profile of Hydroxyl Radicals on BDD
Electrode ............................................. 244
10.4.1 HO" Concentration Profile during Oxygen
Evolution ...................................... 244
10.4.2 HO" Concentration Profile during Electro-
Oxidation of Organic Compound .................. 246
10.5 Kinetic Model of Organics Oxidation on BDD Anode ...... 248
10.5.1 Electrolysis under Current Limited Control
(japplied < jlim) ............................... 249
10.5.2 Electrolysis under Mass Transport Control
(japplied > jlim) ............................... 251
10.6 Electrochemically Induced Mineralization of Organic
Compounds by Molecular Oxygen ......................... 253
10.7 Conclusions ........................................... 256
10.8 Exercises ............................................. 256
10.8.1 Solutions ..................................... 257
References ................................................. 260
11 Modeling of Electrochemical Process for Water Treatment
Using Diamond Films ........................................ 261
Onofrio Scialdone and Alessandro Galia
11.1 Introduction .......................................... 261
11.2 Theoretical Models .................................... 263
11.2.1 General Considerations ......................... 263
11.2.2 Oxidation of Organic Pollutants in Water at
BDD by Means of Direct Anodic Oxidation or
Reaction with Electro-Generated Hydroxyl
Radicals ("Direct Processes") .................. 265
11.2.2.1 The Model of Comninellis and
Coauthors ............................. 268
11.2.2.2 The Theoretical Works ofPolcaro and
Coauthors ............................. 272
11.2.2.3 The Approach Proposed by Rodrigo and
Coauthors ............................. 273
11.2.3 Oxidation of Organic Pollutants in Water by
Means of Electro-Generated Oxidants
("Indirect Processes") Such as Active
Chlorine ....................................... 274
11.3 Conclusions ........................................... 278
11.4 Acknowledgments ....................................... 279
References ................................................. 279
12 Production of Strong Oxidizing Substances with BDD Anodes .. 281
Ana Sánchez-Carretew, Cristina Sáez, Pablo Ca ñizares,
and Manuel A. Rodrigo
12.1 Electrolyses with Conductive-Diamond Anodes ........... 281
12.2 Production and Storage of Oxidizing Substances:
Experimental Setups ................................... 283
12.3 Production of Hydroxyl Radicals with Conductive-
Diamond Anodes ........................................ 284
12.4 Synthesis of Peroxoacids and Peroxosalts .............. 288
12.4.1 Peroxosulphuric Acids .......................... 288
12.4.2 Peroxodiphosphate Salts ........................ 292
12.4.3 Monoperoxophosphoric Acid ...................... 296
12.5 Synthesis of Halogen Oxoanions ........................ 300
12.5.1 Perchlorates ................................... 300
12.5.2 Perbromates .................................... 300
12.6 Synthesis of Ferrates ................................. 301
12.7 Effect of the Type of Diamond on the Efficiency of
the Production of Oxidants ............................ 305
12.8 Conclusions ........................................... 307
12.9 Acknowledgments ....................................... 308
References ................................................. 308
13 Ozone Generation Using Boron-Doped Diamond Electrodes ...... 311
Yunny Meas, Luis A. Godinez, and Erika Bustos
13.1 Introduction .......................................... 311
13.2 Ozone ................................................. 311
13.2.1 Physical and Chemical Properties of Ozone ...... 312
13.2.2 Production of Ozone ............................ 313
13.2.3 Importance of Ozone Applications .............. 313
13.2.4 Efficiency and Production ...................... 315
13.3 Technologies for Producing Ozone ...................... 317
13.3.1 Corona Discharge Technique ..................... 317
13.3.2 Electrical Discharge Ozone Generators (EDOGs) .. 319
13.3.3 Electrolytic Ozone Generators (ELOGs) .......... 319
13.3.3.1 Anodes for Electrochemically
Producing Ozone ....................... 320
13.3.3.2 Boron-Doped Diamond (BDD) ............. 323
13.4 Reaction Mechanism for the Production of Ozone with
Boron-Doped Diamond ................................... 325
13.5 Conclusions ........................................... 326
References ................................................. 327
14 Application of Synthetic Diamond Films to Electro-
Oxidation Processes ........................................ 333
Marco Panizza
14.1 Introduction .......................................... 333
14.2 Application in Wastewater Treatment ................... 335
14.2.1 Oxidation in the Potential Region before
Oxygen Evolution ............................... 335
14.2.2 Oxidation in the Potential Region of Oxygen
Evolution ...................................... 339
14.2.3 Influence of the Nature of Organic Pollutants .. 342
14.2.4 Influence of the Concentrations of Organic
Compounds ...................................... 343
14.2.5 Influence of the Applied Current Density ....... 343
14.2.6 Influence of the Flow Rate ..................... 345
14.2.7 Influence of the Temperature ................... 345
14.2.8 Comparison with Other Electrode Materials ...... 346
14.3 Application in Organic Electrosynthesis ............... 347
14.4 Conclusions ........................................... 348
References ................................................. 349
15 Fabrication and Application of Ti/BDD for Wastewater
Treatment .................................................. 353
Xueming Chen and Guohua Chen
15.1 Fabrication of Stable Ti/BBD Electrodes ............... 353
15.1.1 Introduction ................................... 353
15.1.2 HFCVD Facility ................................. 354
15.1.3 HFCVD Parameter Optimization ................... 354
15.1.4 Reactive Gas Component Improvement ............. 357
15.1.5 Methods to Enhance the Service Life of Ti/BDD .. 363
15.2 Use of Ti/BDD Electrodes for Wastewater Treatment ..... 365
15.2.1 Oxidation of Acetic and Maleic Acids ........... 365
15.2.2 Oxidation of Phenol ............................ 365
15.2.3 Oxidation of Dyes .............................. 366
15.3 Conclusions ........................................... 369
References ................................................. 369
16 Application of Diamond Films to Water Disinfection
Jessica H. Bezerra Rocha and Carlos A. Martínez-Huitle
16.1 Introduction .......................................... 373
16.2 Disinfection Water .................................... 374
16.3 Science and Technology for Water Purification ......... 375
16.4 Electrochemical Disinfection/Purification Systems ..... 376
16.5 Diamond Films for Drinking Water Disinfection ......... 384
16.6 Production of Inorganic Disinfection by-Products and
Inorganic Species Elimination ......................... 388
16.6.1 Chloride, Chlorite, and Chlorate Ions .......... 389
16.6.2 Perchlorate in Drinking Water .................. 392
16.6.3 Electrolysis of Nitrates ....................... 394
16.7 Electrochemical Free-Chlorine Systems Using Diamond
Films ................................................. 396
16.8 Conclusions ........................................... 400
References ................................................. 400
17 Fenton-Electrochemical Treatment of Wastewaters for the
Oxidation of Organic Pollutants Using BDD .................. 405
Enric Brillas
17.1 Introduction .......................................... 405
17.2 Fundamentals of Fenton's Electrochemistry ............. 406
17.3 Electrogeneration of H2O2 and Regeneration of Fe2+ .... 409
17.4 Degradation of Organics in BDD/O2 Tank Reactors ....... 413
17.4.1 Herbicides ..................................... 414
17.4.2 Dyes ........................................... 417
17.4.3 Pharmaceuticals and Amino Acids Precursors ..... 420
17.5 Degradation of Organics in others Tank Reactors with
a BBD Anode ........................................... 426
17.6 Degradation of Organics in Batch Recirculation
BDD/O2 Flow Cells ..................................... 427
17.7 Conclusions ........................................... 433
References ................................................. 433
18 Electrochemical Energy Storage and Energy Conversion
Systems with Diamond Films ................................. 437
Juan M. Peralta-Hernández, Aracely Hernández-Ramírez,
Jorge L. Guzmán-Mar, Laura Hinojosa-Reyes, Giancarlo
R. Salazar-Banda, and Carlos A. Martínez-Huitle
18.1 Introduction .......................................... 437
18.2 Different Techniques Used to Modify BDD Films ......... 438
18.2.1 Microemulsion Synthesis ........................ 438
18.2.2 Thermal Deposition ............................. 443
18.2.3 Electrodeposition .............................. 446
18.2.3.1 Electrodeposition of Metal
Particles on BDD ...................... 449
18.2.4 Sol-Gel Modification ........................... 453
18.3 Application of Modified BDD Films as
Electrocatalytic Surfaces for Fuel Cells .............. 459
18.4 Application of BDD Films in Batteries ................. 466
18.5 Application of BDD Electrodes as Electrochemical
Capacitors ............................................ 474
18.6 Conclusions ........................................... 477
References ................................................. 478
19 Use of Diamond Films in Organic Electrosynthesis ........... 483
Siegfried R. Waldvogel, Axel Kirste, and Stamo Mentizi
19.1 Introduction .......................................... 483
19.2 Specific Features of BDD Electrodes ................... 485
19.3 Stability of BDD Electrodes in Organic Media .......... 487
19.4 Electrolysis Cells for BDD Electrodes for Organic
Transformations ....................................... 489
19.5 Anodic Transformations on BBD Electrodes .............. 491
19.5.1 Alkoxylation Reactions ......................... 491
19.5.2 Fluorination Reactions ......................... 493
19.5.3 Cyanation Reactions ............................ 494
19.5.4 Cleavage of C, C-Bonds ......................... 495
19.5.5 Oxidation of Activated Carbon Atoms ............ 496
19.5.6 Anodic Phenol Coupling Reaction ................ 496
19.5.6.1 Anodic Homo-Coupling of Phenolic
Substrates ............................ 497
19.5.6.2 Nonsymmetrical Phenol Coupling and
Phenol-Arene Cross-Coupling Reaction .. 499
19.6 Cathodic Synthesis on BDD Electrodes .................. 504
19.6.1 Reduction of Oximes ............................ 504
19.6.2 Reductive Carboxylation ........................ 505
19.7 Conclusions ........................................... 506
19.8 Acknowledgment ........................................ 506
References ................................................. 507
PART V BIOELECTROCHEMICAL APPLICATIONS ........................ 511
20 Diamond Sensors for Neurochemistry ......................... 513
Bhavik Anil Patel
20.1 Introduction .......................................... 513
20.2 Central and Peripheral Nervous System ................. 513
20.3 The Process of Neurotransmission ...................... 514
20.3.1 Neurotransmitters .............................. 516
20.4 Electroanalytical Methods to Study Neurotransmitter
Release ............................................... 517
20.4.1 Sensors Utilized ............................... 519
20.5 Limitations of Current Techniques for In Vitro and
In Vivo Monitoring .................................... 520
20.5.1 Long-Term Recordings ........................... 521
20.5.2 Fouling from Large Biomolecules ................ 523
20.5.3 Fouling from Redox Reaction By-Products ........ 525
20.6 Applications of Diamond Sensors and Devices in
Neurochemistry ........................................ 529
20.6.1 Recording Neuronal Activity .................... 529
20.6.2 Single Cell Measurements of Vesicular Release .. 530
20.6.3 Neurotransmitter Release from Sympathetic
Nerves Innervating Mesenteric Arteries ......... 531
20.6.4 Measuring Transmitter Release from the
Gastrointestinal Tract ......................... 533
20.6.4.1 Detection of Histamine Release from
Enterochromaffin-Like Cells Located
in the Stomach ........................ 534
20.6.4.2 Monitoring Serotonin Release from
Enterochromaffin Cells Located in
the Mucosa ............................ 535
20.6.4.3 Monitoring Nitric Oxide Release
from Myenteric Plexus Neurons ......... 537
20.6.5 Studying the Neurotransmitter Clearance
Process ........................................ 538
20.6.5.1 Measurements of Multiple
Transmitters from Brain Synaptosomes .. 539
20.6.5.2 Investigation ofSerotonine Clearance
by Transporters Present on
Lymphocytes ........................... 540
20.6.6 In vitro and In vivo Measurements from the
Central Nervous System ......................... 541
20.6.6.1 In vitro Measurements ................. 541
20.6.6.2 In vivo Measurements from
Anesthetized Animals .................. 542
20.7 Conclusions and Outlook for the Future ................ 543
20.8 Acknowledgments ....................................... 544
References ................................................. 544
21 DNA-Modified Diamond Films ................................. 551
Nianjun Yang and Christoph E. Nebel
21.1 Introduction .......................................... 551
21.2 Diamond Transducer Properties ......................... 558
21.2.1 CVD Diamond Growth ............................. 558
21.2.2 Surface Terminations ........................... 562
21.2.3 Diamond Nanotexture and Wire Formation ......... 564
21.3 Surface Modification of Diamond ....................... 571
21.3.1 Photochemical Surface Modification of
Intrinsic Diamond .............................. 571
21.3.2 Electrochemical Surface Functionalization of
Boron-Doped Diamond ............................ 582
21.3.3 Tip Functionalization of Diamond Nanotextures .. 589
21.4 DNA Molecules on Diamond .............................. 593
21.4.1 DNA Attachment ................................. 593
21.4.2 Characterizations of DNA Layers ................ 595
21.5 Sensing of DNA Hybridization .......................... 602
21.5.1 DNA Field Effect Transistor .................... 602
21.5.2 Cyclic Voltammetry and Impedance Spectroscopy .. 606
21.5.3 DNA Sensing on Nanotextured Diamond Surfaces ... 609
21.6 Summary and Outlook ................................... 612
21.7 Acknowledgments ....................................... 614
References ................................................. 614
INDEX ......................................................... 621
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