Advanced Electrode Materials

This book covers the recent advances in electrode materials and their novel applications at the cross-section of advanced materials. The book is divided into two sections: State-of-the-art electrode materials; and engineering of applied electrode materials. The chapters deal with electrocatalysis for energy conversion in view of bionanotechnology; surfactant-free materials and polyoxometalates through the concepts of biosensors to renewable energy applications; mesoporous carbon, diamond, conducting polymers and tungsten oxide/conducting polymer-based electrodes and hybrid systems. Numerous approaches are reviewed for lithium batteries, fuel cells, the design and construction of anode for microbial fuel cells including phosphate polyanion electrodes, electrocatalytic materials, fuel cell reactions, conducting polymer based hybrid nanocomposites and advanced nanomaterials.

Ashutosh Tiwari is Secretary General, International Association of Advanced Materials; Chairman and Managing Director of Tekidag AB (Innotech); Associate Professor and Group Leader, Smart Materials and Biodevices at the world premier Biosensors and Bioelectronics Centre, IFM-Linköping University; Editor-in-Chief, Advanced Materials Letters; a materials chemist and docent in the Applied Physics with the specialization of Biosensors and Bioelectronics from Linköping University, Sweden. He has more than 100 peer-reviewed primary research publications in the field of materials science and nanotechnology and has edited/authored more than 35 books on advanced materials and technology.

Feliz Kuralay is currently at Ordu University, Turkey.

Lokman Uzun is an Associate Professor at the Department of Chemistry, Biochemistry Division, Hacettepe University, Ankara, Turkey where he also received his PhD in 2008. He is the author of more than 75 articles in peer-review journals and is the Assistant Editor of Hacettepe’s Journal of Biology and Chemistry. He recently took up a fellowship with the Biosensors and Bioelectronics Centre, Linköping University, Sweden. His research interest is mainly in materials science, surface modification, affinity interaction, polymer science, especially molecularly imprinted polymers and their applications in biosensors, bioseparation, food safety, and the environmental sciences.

Preface xv

Part 1 State-of-the-art electrode materials

1 Advances in Electrode Materials 3
J. Sołoducho, J. Cabaj and D. Zając

1.1 Advanced Electrode Materials for Molecular Electrochemistry 4

1.1.1 Graphite and Related sp2-Hybridized Carbon Materials 4

1.1.2 Graphene 6

1.1.2.1 Graphene Preparation 6

1.1.2.2 Engineering of Graphene 7

1.1.3 Carbon Nanotubes 8

1.1.3.1 Carbon Nanotube Networks for Applications in Flexible Electronics 9

1.1.4 Surface Structure of Carbon Electrode Materials 11

1.2 Electrode Materials for Electrochemical Capacitors 12

1.2.1 Carbon-based Electrodes 12

1.2.2 Metal Oxide Composite Electrodes 13

1.2.3 Conductive Polymers-based Electrodes 15

1.2.4 Nanocomposites-based Electrode Materials for Supercapacitor 16

1.3 Nanostructure Electrode Materials for Electrochemical Energy Storage and Conversion 16

1.3.1 Assembly and Properties of Nanoparticles 17

1.4 Progress and Perspective of Advanced Electrode Materials 18

Acknowledgments 19

References 19

2 Diamond-based Electrodes 27
Emanuela Tamburri and Maria Letizia Terranova

2.1 Introduction 27

2.2 Techniques for Preparation of Diamond Layers 28

2.2.1 HF-CVD Diamond Synthesis 30

2.2.2 MW-CVD Diamond Synthesis 31

2.2.3 RF-CVD Diamond Synthesis 31

2.3 Why Diamond for Electrodes? 32

2.4 Diamond Doping 33

2.4.1 In Situ Diamond Doping 34

2.4.2 Ion Implantation 37

2.5 Electrochemical Properties of Doped Diamonds 37

2.6 Diamond Electrodes Applications 39

2.6.1 Water Treatment and Disinfection 39

2.6.2 Electroanalytical Sensors 40

2.6.3 Energy Technology 45

2.6.3.1 Supercapacitors 45

2.6.3.2 Li Ion Batteries 49

2.6.3.3 Fuel Cells 51

2.7 Conclusions 52

References 53

3 Recent Advances in Tungsten Oxide/Conducting Polymer Hybrid Assemblies for Electrochromic Applications 61
Cigdem Dulgerbaki and Aysegul Uygun Oksuz

3.1 Introduction 62

3.2 History and Technology of Electrochromics 63

3.3 Electrochromic Devices 63

3.3.1 Electrochromic Contrast 64

3.3.2 Coloration Efficiency 64

3.3.3 Switching Speed 65

3.3.4 Stability 65

3.3.5 Optical Memory 65

3.4 Transition Metal Oxides 67

3.5 Tungsten Oxide 67

3.6 Conjugated Organic Polymers 69

3.7 Hybrid Materials 70

3.8 Electrochromic Tungsten Oxide/Conducting Polymer Hybrids 71

3.9 Conclusions and Perspectives 95

Acknowledgments 99

References 99

Contents vii

4 Advanced Surfactant-free Nanomaterials for Electrochemical Energy Conversion Systems: From Electrocatalysis to Bionanotechnology 103
Yaovi Holade, Teko W. Napporn and Kouakou B. Kokoh

4.1 Advanced Electrode Materials Design: Preparation and Characterization of Metal Nanoparticles 104

4.1.1 Current Strategies for Metal Nanoparticles Preparation: General Consideration 104

4.1.2 Emerged Synthetic Methods without Organic Molecules as Surfactants 109

4.2 Electrocatalytic Performances Toward Organic Molecules Oxidation 114

4.2.1 Electrocatalytic Properties of Metal Nanoparticles in Alkaline Medium 114

4.2.1.1 Electrocatalytic Properties Toward Glycerol Oxidation 114

4.2.1.3 Electrocatalytic Properties Toward Carbohydrates Oxidation 116

4.2.2 Spectroelectrochemical Characterization of the Electrode–Electrolyte Interface 118

4.2.2.1 Spectroelectrochemical Probing of Electrode Materials Surface by CO Stripping 118

4.2.2.2 Spectroelectrochemical Probing of Glycerol Electrooxidation Reaction 120

4.2.2.3 Spectroelectrochemical Probing of Glucose Electrooxidation Reaction 121

4.2.3 Electrochemical Synthesis of Sustainable Chemicals: Electroanalytical Study 123

4.2.4 Electrochemical Energy Conversion: Direct Carbohydrates Alkaline Fuel Cells 128

4.3 Metal Nanoparticles at Work in Bionanotechnology 131

4.3.1 Metal Nanoparticles at Work in Closed-Biological Conditions: Toward Implantable Devices 131

4.3.2 Activation of Implantable Biomedical and Information Processing Devices by Fuel Cells 133

4.4 Conclusions 136

Acknowledgments 137

Notes 137

References 138

Part 2 Engineering of applied electrode materials

5 Polyoxometalate-based Modified Electrodes for Electrocatalysis: From Molecule Sensing to Renewable Energy-related Applications 149
Cristina Freire, Diana M. Fernandes, Marta Nunes and Mariana Araújo

5.1 Introduction 150

5.2 POM and POM-based (Nano)Composites 151

5.2.1 Polyoxometalates 151

5.2.2 Polyoxometalate-based (Nano)Composites 154

5.2.3 General Electrochemical Behavior of POMs 157

5.3 POM-based Electrocatalysis for Sensing Applications 160

5.3.1 Reductive Electrocatalysis 161

5.3.1.1 Nitrite Reduction 161

5.3.1.2 Bromate Reduction 167

5.3.1.3 Iodate Reduction 168

5.3.1.4 Hydrogen Peroxide Reduction Reaction 170

5.3.2 Oxidative Electrocatalysis 173

5.3.2.1 Dopamine and Ascorbic Acid Oxidations 173

5.3.2.2 l-Cysteine Oxidation 177

5.4 POM-based Electrocatalysis for Energy Storage and Conversion Applications 178

5.4.1 Oxygen Evolution Reaction 179

5.4.2 Hydrogen Evolution Reaction 183

5.4.3 Oxygen Reduction Reaction 185

5.5 Concluding Remarks 191

Acknowledgments 193

List of Abbreviations and Acronyms 193

References 196

6 Electrochemical Sensors Based on Ordered Mesoporous Carbons 213
Xiangjie Bo and Ming Zhou

6.1 Introduction 213

6.2 Electrochemical Sensors Based on OMCs 217

6.3 Electrochemical Sensors Based on Redox Mediators/OMCs 222

6.4 Electrochemical Sensors Based on NPs/OMCs 226

6.4.1 Electrochemical Sensors Based on Transition Metal NPs/OMCs 228

6.4.2 Electrochemical Sensors Based on Noble Metal NPs/OMCs 230

6.5 Conclusions 233

Acknowledgments 236

References 236

7 Non-precious Metal Oxide and Metal-free Catalysts for Energy Storage and Conversion 243
Tahereh Jafari, Andrew Meguerdichian, Ting Jiang, Abdelhamid El-Sawy and Steven L. Suib

7.1 Metal–Nitrogen–Carbon (M–N–C) Electrocatalysts 244

7.1.1 Introduction 244

7.1.2 Catalysts for Hydrogen Evolution Reaction 245

7.1.3 Catalysts for Oxygen Evolution Reaction 248

7.1.4 Catalysts for Oxygen Reduction Reaction 249

7.1.5 None-Heat-treated M–N–C Electrocatalysts 250

7.1.6 Heat-treated M–N–C Electrocatalysts 254

7.1.7 Conclusion 261

7.2 Transition Metal Oxide Electrode Materials for Oxygen Evolution Reaction, Oxygen Reduction Reaction and Bifuctional Purposes (OER/ORR) 262

7.2.1 Introduction 262

7.2.2 Oxygen Evolution Reaction 266

7.2.2.1 Synthesis Methodology 267

7.2.2.2 OER Properties of Catalyst 272

7.2.2.3 Morphology or Microstructure Analysis of TM Oxide for OER 274

7.2.3 Oxygen Reduction Reaction 276

7.2.3.1 Morphology or Microstructure Analysis 277

7.2.3.2 ORR Properties of Catalyst 278

7.2.3.3 Synthesis Methodology 278

7.2.3.4 Theoretical Analyses of ORR Active Catalysts 279

7.2.4 Hydrogen Evolution Reaction 279

7.2.5 Bifunctional Oxide Materials (OER/ORR) 281

7.2.5.1 Bifunctional Properties of Catalyst 281

7.2.5.2 Dopant Effects 283

7.2.5.3 Morphology or Microstructure Analysis 283

7.2.5.4 Synthesis Methodology 284

7.2.6 Conclusion 285

7.3 Transition Metal Chalcogenides, Nitrides, Oxynitrides, and Carbides (By: Ting Jiang) 285

7.3.1 Transition Metal Chalcogenides 285

7.3.2 Transition Metal Nitrides 294

7.3.3 Transition Metal Oxynitrides 296

7.3.4 Transition Metal Carbides 298

7.4 Oxygen Reduction Reaction for Metal-free 300

7.4.1 Different Doping Synthesis Strategies 300

7.4.2 ORR Activity in Different Carbon Source 303

7.4.2.1 1D Carbon Nanotube Doped 303

7.4.2.2 2D Graphene 306

7.4.3 Oxygen Evolution Reaction 308

References 310

8 Study of Phosphate Polyanion Electrodes and Their Performance with Glassy Electrolytes: Potential Application in Lithium Ion Solid-state Batteries 321
S. Terny and M.A. Frechero

8.1 Introduction 321

8.2 Glass Samples Preparation 323

8.3 Nanostructured Composites Sample Preparation 324

8.4 X-Ray Powder Diffraction 325

8.4.1 X-Ray Powder Diffraction Patterns of Glassy Materials 325

8.4.2 X-Ray Powder Diffraction Patterns of Composites Materials 326

8.5 Thermal Analysis 326

8.5.1 Thermal Analysis of Glassy Systems 326

8.5.2 Thermal Analysis of Nanocomposites Materials 329

8.6 Density and Appearance 330

8.6.1 Density and Oxygen Packing Density of Glassy Materials 330

8.6.2 Materials’ Appearance 331

8.6.2.1 Glasses 331

8.6.2.2 Nanostructured Composites 332

8.7 Structural Features 332

8.7.1 Glassy Materials 332

8.7.1.1 FTIR and Raman Spectroscopy 334

8.7.2 Nanocomposites Materials 337

8.8 Electrical Behavior 342

8.8.1 Glasses Materials 342

8.8.2 Composite Materials 347

8.9 All-solid-state Lithium Ion Battery 349

8.10 Final Remarks 350

Acknowledgments 352

References 352

9 Conducting Polymer-based Hybrid Nanocomposites as Promising Electrode Materials for Lithium Batteries 355
O.Yu. Posudievsky, O.A. Kozarenko, V.G. Koshechko and V.D. Pokhodenko

9.1 Introduction 356

9.2 Electrode Materials of Lithium Batteries Based on Conducting Polymer-based Nanocomposites Prepared by Chemical and Electrochemical Methods 357

9.2.1 Host–Guest Hybrid Nanocomposites 357

9.2.2 Core–Shell Hybrid Nanocomposites 361

9.3 Mechanochemical Preparation of Conducting Polymer-based Hybrid Nanocomposites as Electrode Materials of Lithium Batteries 368

9.3.1 Principle of Mechanochemical Synthesis 368

9.3.2 Mechanochemically Prepared Conducting Polymer-based Hybrid Nanocomposite Materials for Lithium Batteries 370

9.4 Conclusion 384

References 385

10 Energy Applications: Fuel Cells 397
Mutlu Sönmez Çelebi

10.1 Introduction 398

10.2 Catalyst Supports for Fuel Cell Electrodes 399

10.2.1 Commercial Carbon Supports 399

10.2.2 Carbon Nanotube (CNT) Supports 401

10.2.3 Graphene Supports 403

10.2.4 Mesoporous Carbon Supports 405

10.2.5 Other Carbon Supports 406

10.2.6 Conducting Polymer Supports 408

10.2.7 Hybrid Supports 410

10.2.8 Non-carbon Supports 411

References 421

11 Novel Photoelectrocatalytic Electrodes Materials for Fuel Cell Reactions 435
Mingshan Zhu, Chunyang Zhai and Cheng Lu

11.1 Introduction 435

11.2 Basic Understanding on the Improved Catalytic Performance of Photo-Responsive Metal/ Semiconductor Electrodes 438

11.3 Synthetic Methods for Metal/Semiconductor Electrodes 440

11.3.1 Electrochemical Deposition 441

11.3.2 Chemical Reduction Method 442

11.3.3 Physical Mixing Method 443

11.3.4 Hydrothermal/Solvothermal Method 444

11.3.5 Microwave-assisted Method 445

11.3.6 Other Preparation Methods 445

11.4 Photo-responsive Metal/Semiconductor Anode Catalysts 446

11.4.1 TiO2 Nanoparticles 446

11.4.2 One-dimensional Well-aligned TiO2 Nanotube Arrays 448

11.4.3 Other Semiconductor Supports 450

11.5 Conclusions and Future Outlook 452

References 453

12 Advanced Nanomaterials for the Design and Construction of Anode for Microbial Fuel Cells 457
Ming Zhou, Lu Bai and Chaokang Gu

12.1 Introduction 457

12.2 Carbon Nanotubes-based Anode Materials for MFCs 459

12.3 Graphene-based Anode Materials for MFCs 466

12.4 Other Anode Materials for MFCs 470

12.5 Conclusions 474

Acknowledgments 475

References 475

13 Conducting Polymer-based Electrochemical DNA Biosensing 485
Filiz Kuralay

13.1 Introduction 486

13.2 Electrochemical DNA Biosensors 487

13.3 Conducting Polymer-based Electrochemical DNA Biosensors 489

13.4 Conclusions and Outlook 493

Acknowledgments 494

References 494

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