Enzymatic Fuel Cells: From Fundamentals to Applications / Edition 1

Enzymatic Fuel Cells: From Fundamentals to Applications / Edition 1

ISBN-10:
1118369238
ISBN-13:
9781118369234
Pub. Date:
05/27/2014
Publisher:
Wiley
ISBN-10:
1118369238
ISBN-13:
9781118369234
Pub. Date:
05/27/2014
Publisher:
Wiley
Enzymatic Fuel Cells: From Fundamentals to Applications / Edition 1

Enzymatic Fuel Cells: From Fundamentals to Applications / Edition 1

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Overview

Summarizes research encompassing all of the aspects required to understand, fabricate and integrate enzymatic fuel cells

  • Contributions span the fields of bio-electrochemistry and biological fuel cell research
  • Teaches the reader to optimize fuel cell performance to achieve long-term operation and realize commercial applicability
  • Introduces the reader  to the scientific aspects of bioelectrochemistry including electrical wiring of enzymes and charge transfer in enzyme fuel cell electrodes
  • Covers unique engineering problems of enzyme fuel cells such as design and optimization

Product Details

ISBN-13: 9781118369234
Publisher: Wiley
Publication date: 05/27/2014
Pages: 496
Product dimensions: 6.20(w) x 9.40(h) x 1.20(d)

About the Author

HEATHER R. LUCKARIFT is the Senior Research Scientist for Universal Technology Corporation at the Air Force Civil Engineer Center (formerly the Microbiology & Applied Biochemistry team at the Air Force Research Laboratory). She is the author of over fifty peer-reviewed publications and invited reviews.

PLAMEN ATANASSOV is a Professor of Chemical & Nuclear Engineering and the founding director of The University of New Mexico Center for Emerging Energy Technologies. He was the principal investigator on an Air Force Office of Scientific Research Multi-University Research Initiative program: “Fundamentals and Bioengineering of Enzymatic Fuel Cells.” He is the author of more than 220 publications, including twelve reviews.

GLENN R. JOHNSON is the Chief Scientist and founder of Hexpoint Technologies and the former principal investigator of the Microbiology & Applied Biochemistry team within the Air Force Research Laboratory. He is the author of over fifty peer-reviewed publications and invited reviews.

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Table of Contents

Preface xv

Contributors xvii

1 Introduction 1
Heather R. Luckarift, Plamen Atanassov, and Glenn R. Johnson

List of Abbreviations, 3

2 Electrochemical Evaluation of Enzymatic Fuel Cells and Figures of Merit 4
Shelley D. Minteer, Heather R. Luckarift, and Plamen Atanassov

2.1 Introduction, 4

2.2 Electrochemical Characterization, 5

2.2.1 Open-Circuit Measurements, 5

2.2.2 Cyclic Voltammetry, 5

2.2.3 Electron Transfer, 6

2.2.4 Polarization Curves, 6

2.2.5 Power Curves, 8

2.2.6 Electrochemical Impedance Spectroscopy, 8

2.2.7 Multienzyme Cascades, 8

2.2.8 Rotating Disk Electrode Voltammetry, 9

2.3 Outlook, 9

Acknowledgment, 10

List of Abbreviations, 10

References, 10

3 Direct Bioelectrocatalysis: Oxygen Reduction for Biological Fuel Cells 12
Dmitri M. Ivnitski, Plamen Atanassov, and Heather R. Luckarift

3.1 Introduction, 12

3.2 Mechanistic Studies of Intramolecular Electron Transfer, 13

3.2.1 Determining the Redox Potential of MCO, 13

3.2.2 Effect ofpHand Inhibitors on the Electrochemistry ofMCO, 17

3.3 Achieving DET of MCO by Rational Design, 18

3.3.1 Surface Analysis of Enzyme-Modified Electrodes, 20

3.3.2 Design of MCO-Modified Biocathodes Based on Direct Bioelectrocatalysis, 21

3.3.3 Design of MCO-Modified “Air-Breathing” Biocathodes, 22

3.4 Outlook, 25

Acknowledgments, 26

List of Abbreviations, 26

References, 27

4 Anodic Catalysts for Oxidation of Carbon-Containing Fuels 33
Rosalba A. Rincón, Carolin Lau, Plamen Atanassov, and Heather R. Luckarift

4.1 Introduction, 33

4.2 Oxidases, 34

4.2.1 Electron Transfer Mechanisms of Glucose Oxidase, 34

4.3 Dehydrogenases, 35

4.3.1 The NADH Reoxidation Issue, 35

4.3.2 Mediators for Electrochemical Oxidation of NADH, 37

4.3.3 Electropolymerization of Azines, 38

4.3.4 Alcohol Dehydrogenase as a Model System, 41

4.4 PQQ-Dependent Enzymes, 42

4.5 Outlook, 44

Acknowledgment, 45

List of Abbreviations, 45

References, 45

5 Anodic Bioelectrocatalysis: From Metabolic Pathways to Metabolons 53
Shuai Xu, Lindsey N. Pelster, Michelle Rasmussen, and Shelley D. Minteer

5.1 Introduction, 53

5.2 Biological Fuels, 53

5.3 Promiscuous Enzymes Versus Multienzyme Cascades Versus Metabolons, 55

5.3.1 Promiscuous Enzymes, 55

5.3.2 Multienzyme Cascades, 56

5.3.3 Metabolons, 56

5.4 Direct and Mediated Electron Transfer, 57

5.5 Fuels, 58

5.5.1 Hydrogen, 58

5.5.2 Ethanol, 58

5.5.3 Methanol, 60

5.5.4 Methane, 61

5.5.5 Glucose, 61

5.5.6 Sucrose, 65

5.5.7 Trehalose, 65

5.5.8 Fructose, 67

5.5.9 Lactose, 68

5.5.10 Lactate, 68

5.5.11 Pyruvate, 69

5.5.12 Glycerol, 70

5.5.13 Fatty Acids, 70

5.6 Outlook, 72

Acknowledgment, 72

List of Abbreviations, 73

References, 73

6 Bioelectrocatalysis of Hydrogen Oxidation/Reduction by Hydrogenases 80
Anne K. Jones, Arnab Dutta, Patrick Kwan, Chelsea L. McIntosh, Souvik Roy, and Sijie Yang

6.1 Introduction, 80

6.2 Hydrogenases, 81

6.3 Biological Fuel Cells Using Hydrogenases: Electrocatalysis, 85

6.4 Electrocatalysis by Functional Mimics of Hydrogenases, 92

6.4.1 [FeFe]-Hydrogenase Models, 92

6.4.2 [NiFe]-Hydrogenase Models, 95

6.4.3 Incorporation of Outer Coordination Sphere Features, 97

6.5 Outlook, 97

Acknowledgments, 98

List of Abbreviations, 98

References, 99

7 Protein Engineering for Enzymatic Fuel Cells 109
Elliot Campbell and Scott Banta

7.1 Engineering Enzymes for Catalysis, 109

7.2 Engineering Other Properties of Enzymes, 112

7.2.1 Stability, 112

7.2.2 Size, 113

7.2.3 Cofactor Specificity, 113

7.3 Enzyme Immobilization and Self-Assembly, 115

7.3.1 Engineering for Supermolecular Assembly, 116

7.4 Artificial Metabolons, 117

7.4.1 DNA-Templated Metabolons, 117

7.5 Outlook, 118

List of Abbreviations, 118

References, 118

8 Purification and Characterization of Multicopper Oxidases for Enzyme Electrodes 123
D. Matthew Eby and Glenn R. Johnson

8.1 Introduction, 123

8.2 General Considerations for MCO Expression and Purification, 124

8.3 MCO Production and Expression Systems, 125

8.4 MCO Purification, 128

8.5 Copper Stability and Specific Considerations for MCO Production, 133

8.6 Spectroscopic Monitoring and Characterization of Copper Centers, 136

8.7 Outlook, 139

Acknowledgment, 140

List of Abbreviations, 140

References, 140

9 Mediated Enzyme Electrodes 146
Joshua W. Gallaway

9.1 Introduction, 146

9.2 Fundamentals, 147

9.2.1 Electron Transfer Overpotentials, 147

9.2.2 Electron Transfer Rate, 151

9.2.3 Enzyme Kinetics, 151

9.3 Types of Mediation, 152

9.3.1 Freely Diffusing Mediator in Solution, 152

9.3.2 Mediation in Cross-Linked Redox Polymers, 154

9.3.3 Further Redox Polymer Mediation, 156

9.3.4 Mediation in Other Immobilized Layers, 160

9.4 Aspects of Mediator Design I: Mediator Overpotentials, 162

9.4.1 Considering Species Potentials in a Methanol–Oxygen BFC, 162

9.4.2 The Earliest Methanol-Oxidizing BFC Anodes, 162

9.4.3 A Four-Enzyme Methanol-Oxidizing Anode, 164

9.5 Aspects of Mediator Design II: Saturated Mediator Kinetics, 165

9.5.1 An Immobilized Laccase Cathode, 166

9.5.2 Potential of the Osmium Redox Polymer, 167

9.5.3 Concentration of Redox Sites in the Mediator Film, 170

9.6 Outlook, 172

List of Abbreviations, 172

References, 172

10 Hierarchical Materials Architectures for Enzymatic Fuel Cells 181
Guinevere Strack and Glenn R. Johnson

10.1 Introduction, 181

10.2 Carbon Nanomaterials and the Construction of the Bio–Nano Interface, 184

10.2.1 Carbon Black Nanomaterials, 184

10.2.2 Carbon Nanotubes, 185

10.2.3 Graphene, 187

10.2.4 CNT-Decorated Porous Carbon Architectures, 188

10.2.5 Buckypaper, 188

10.3 Biotemplating: The Assembly of Nanostructured Biological–Inorganic Materials, 191

10.3.1 Protein-Mediated 3D Biotemplating, 192

10.4 Fabrication of Hierarchically Ordered 3D Materials for Enzyme and Microbial Electrodes, 194

10.4.1 Chitosan–CNT Conductive Porous Scaffolds, 195

10.4.2 Polymer/Carbon Architectures Fabricated Using Solid Templates, 196

10.5 Incorporating Conductive Polymers into Bioelectrodes for Fuel Cell Applications, 198

10.5.1 Conductive Polymer-Facilitated DET Between Laccase and a Conductive Surface, 198

10.5.2 Materials Design for MFC, 200

10.6 Outlook, 201

Acknowledgment, 201

List of Abbreviations, 201

References, 202

11 Enzyme Immobilization for Biological Fuel Cell Applications 208
Lorena Betancor and Heather R. Luckarift

11.1 Introduction, 208

11.2 Immobilization by Physical Methods, 209

11.2.1 Adsorption, 209

11.3 Entrapment as a Pre- and Post-Immobilization Strategy, 211

11.3.1 Stabilization via Encapsulation, 212

11.3.2 Redox Hydrogels, 212

11.4 Enzyme Immobilization via Chemical Methods, 213

11.4.1 Covalent Immobilization, 213

11.4.2 Molecular Tethering, 213

11.4.3 Self-Assembly, 215

11.5 Orientation Matters, 216

11.6 Outlook, 218

Acknowledgment, 219

List of Abbreviations, 219

References, 219

12 Interrogating Immobilized Enzymes in Hierarchical Structures 225
Michael J. Cooney and Heather R. Luckarift

12.1 Introduction, 225

12.2 Estimating the Bound Active (Redox) Enzyme, 227

12.2.1 Modeling the Performance of Immobilized Redox Enzymes in Flow-Through Mode to Estimate the Concentration of Substrate at the Enzyme Surface, 229

12.3 Probing the Distribution of Immobilized Enzyme Within Hierarchical Structures, 232

12.4 Probing the Immediate Chemical Microenvironments of Enzymes in Hierarchical Structures, 235

12.5 Enzyme Aggregation in a Hierarchical Structure, 236

12.6 Outlook, 238

Acknowledgment, 239

List of Abbreviations, 239

References, 239

13 Imaging and Characterization of the Bio–Nano Interface 242
Karen E. Farrington, Heather R. Luckarift, D. Matthew Eby, and Kateryna Artyushkova

13.1 Introduction, 242

13.2 Imaging the Bio–Nano Interface, 243

13.2.1 Scanning Electron Microscopy, 243

13.2.2 Transmission Electron Microscopy, 248

13.3 Characterizing the Bio–Nano Interface, 248

13.3.1 X-Ray Photoelectron Spectroscopy, 248

13.3.2 Surface Plasmon Resonance, 256

13.4 Interrogating the Bio–Nano Interface, 256

13.4.1 Atomic Force Microscopy, 256

13.5 Outlook, 267

Acknowledgment, 267

List of Abbreviations, 267

References, 268

14 Scanning Electrochemical Microscopy for Biological Fuel Cell Characterization 273
Ramaraja P. Ramasamy

14.1 Introduction, 273

14.2 Theory and Operation, 274

14.3 Ultramicroelectrodes, 275

14.3.1 Approach Curve Method of Analysis, 276

14.4 Modes of SECM Operation, 278

14.4.1 Negative Feedback Mode, 278

14.4.2 Positive Feedback Mode, 279

14.4.3 Generation–Collection Mode, 279

14.4.4 Induced Transfer Mode, 280

14.5 SECM for BFC Anodes, 281

14.5.1 Enzyme-Mediated Feedback Imaging, 281

14.5.2 Generation–Collection Mode Imaging, 284

14.6 SECM for BFC Cathodes, 285

14.6.1 Tip Generation–Substrate Collection Mode, 286

14.6.2 Redox Competition Mode, 289

14.7 Catalyst Screening Using SECM, 290

14.8 SECM for Membranes, 291

14.9 Probing Single Enzyme Molecules Using SECM, 293

14.10 Combining SECM with Other Techniques, 293

14.10.1 Atomic Force Microscopy, 294

14.10.2 Confocal Laser Scanning Microscopy, 295

14.11 Outlook, 297

List of Abbreviations, 297

References, 298

15 In Situ X-Ray Spectroscopy of Enzymatic Catalysis: Laccase-Catalyzed Oxygen Reduction 304
Sanjeev Mukerjee, Joseph Ziegelbauer, Thomas M. Arruda, Kateryna Artyushkova, and Plamen Atanassov

15.1 Introduction, 304

15.2 Defining the Enzyme/Electrode Interface, 305

15.3 Direct Electron Transfer Versus Mediated Electron Transfer, 306

15.3.1 Mediated Electron Transfer, 307

15.4 The Blue Copper Oxidases, 308

15.4.1 Laccase, 309

15.5 In Situ XAS, 310

15.5.1 Os L3-Edge, 314

15.5.2 uMET, 317

15.5.3 Mediated Electron Transfer, 319

15.5.4 FEFF8.0 Analysis, 323

15.6 Proposed ORR Mechanism, 327

15.7 Outlook, 331

Acknowledgments, 331

List of Abbreviations, 331

References, 332

16 Enzymatic Fuel Cell Design, Operation, and Application 337
Vojtech Svoboda and Plamen Atanassov

16.1 Introduction, 337

16.2 Biobatteries and EFCs, 338

16.3 Components, 339

16.3.1 Anodes, 339

16.3.2 Cathodes, 340

16.3.3 Separator and Membrane, 341

16.3.4 Reference Electrode, 342

16.3.5 Fuel and Electrolyte, 342

16.4 Single-Cell Design, 345

16.4.1 Design of Single-Cell EFC Compartment, 345

16.5 Microfluidic EFC Design, 348

16.6 Stacked Cell Design, 348

16.6.1 Series-Connected EFC Stack, 348

16.6.2 Parallel-Connected EFC Stack, 349

16.7 Bipolar Electrodes, 350

16.8 Air/Oxygen Supply, 351

16.9 Fuel Supply, 351

16.9.1 Fuel Flow-Through, 352

16.9.2 Fuel Flow-Through System, 354

16.9.3 Fuel Flow-Through Operation and Fuel Waste Management, 355

16.10 Storage and Shelf Life, 356

16.11 EFC Operation, Control, and Integration with Other Power Sources, 356

16.11.1 Activation, 356

16.12 EFC Control, 357

16.13 Power Conditioning, 357

16.14 Outlook, 358

List of Abbreviations, 359

References, 359

17 Miniature Enzymatic Fuel Cells 361
Takeo Miyake and Matsuhiko Nishizawa

17.1 Introduction, 361

17.2 Insertion MEFC, 362

17.2.1 Insertion MEFC with Needle Anode and Gas Diffusion Cathode, 363

17.2.2 Windable, Replaceable Enzyme Electrode Films, 364

17.3 Microfluidic MEFC, 366

17.3.1 Effects of Structural Design on Cell Performances, 366

17.3.2 Automatic Air Valve System, 367

17.3.3 SPG System, 369

17.4 Flexible Sheet MEFC, 370

17.5 Outlook, 371

List of Abbreviations, 372

References, 372

18 Switchable Electrodes and Biological Fuel Cells 374
Evgeny Katz, Vera Bocharova, and Jan Halámek

18.1 Introduction, 374

18.2 Switchable Electrodes for Bioelectronic Applications, 375

18.3 Light-Switchable Modified Electrodes Based on Photoisomerizable Materials, 376

18.4 Magnetoswitchable Electrochemical Reactions Controlled by Magnetic Species Associated with Electrode Interfaces, 378

18.5 Modified Electrodes Switchable by Applied Potentials Resulting in Electrochemical Transformations at Functional Interfaces, 381

18.6 Chemically/Biochemically Switchable Electrodes, 383

18.7 Coupling of Switchable Electrodes with Biomolecular Computing Systems, 389

18.8 BFCs with Switchable/Tunable Power Output, 396

18.8.1 Switchable/Tunable BFCs Controlled by Electrical Signals, 397

18.8.2 Switchable/Tunable BFCs Controlled by Magnetic Signals, 399

18.8.3 BFCs Controlled by Logically Processed Biochemical Signals, 402

18.9 Outlook, 412

Acknowledgments, 413

List of Abbreviations, 413

References, 414

19 Biological Fuel Cells for Biomedical Applications 422
Magnus Falk, Sergey Shleev, Claudia W. Narváez Villarrubia, Sofia Babanova, and Plamen Atanassov

19.1 Introduction, 422

19.2 Definition and Classification of BFCs, 424

19.2.1 Cell- and Organelle-Based Fuel Cells, 425

19.2.2 Enzymatic Fuel Cells, 426

19.3 Design Aspects of EFCs, 427

19.3.1 Electron Transfer, 427

19.3.2 Enzymes, 428

19.3.3 Electrodes and Electrode Materials, 430

19.3.4 Biodevice Design, 431

19.4 In Vitro and In Vivo BFC Studies, 433

19.4.1 In Vitro BFCs, 433

19.4.2 In Vivo Operating BFCs, 435

19.5 Outlook, 440

List of Abbreviations, 442

References, 443

20 Concluding Remarks and Outlook 451
Glenn R. Johnson, Heather R. Luckarift, and Plamen Atanassov

20.1 Introduction, 451

20.2 Primary System Engineering: Design Determinants, 453

20.3 Fundamental Advances in Bioelectrocatalysis, 454

20.4 Design Opportunities from EFC Operation, 454

20.5 Fundamental Drivers for EFC Miniaturization, 455

20.6 Commercialization of EFCs: Strategies and Opportunities, 455

Acknowledgment, 457

List of Abbreviations, 457

References, 457

Index 459

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