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Enzymatic Fuel Cells

From Fundamentals to Applications
1. Aufl.

von: Heather R. Luckarift, Plamen B. Atanassov, Glenn R. Johnson
113,99 €
Verlag:	Wiley
Format:	PDF
Veröffentl.:	16.04.2014
ISBN/EAN:	9781118869864
Sprache:	englisch
Anzahl Seiten:	496

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Beschreibungen

Titelbeschreibung

Summarizes research encompassing all of the aspects required to understand, fabricate and integrate enzymatic fuel cells <ul> <li>Contributions span the fields of bio-electrochemistry and biological fuel cell research</li> <li>Teaches the reader to optimize fuel cell performance to achieve long-term operation and realize commercial applicability</li> <li>Introduces the reader to the scientific aspects of bioelectrochemistry including electrical wiring of enzymes and charge transfer in enzyme fuel cell electrodes</li> <li>Covers unique engineering problems of enzyme fuel cells such as design and optimization</li> </ul>

Inhaltsverzeichnis

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

Autorenportrait

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.

Back cover copy

A thorough and illuminating look at enzymatic fuel cells and their place in our current and future world With their use in biomedical applications and for portable electronics, enzymatic fuel cells offer an alternative power source to meet our world’s increasing energy demands. Outlining the fundamentals, design, optimization, integration, and future trends of enzymatic fuel cells, Enzymatic Fuel Cells: From Fundamentals to Applications presents a comprehensive overview of enzymatic fuel cell research—with a special emphasis on methodology, fabrication, integration, and testing of enzymatic fuel cells. The book provides introductory reading with a concise scheme of illustrations and: <ul> <li>Covers fundamentals of enzymatic fuel cells as well as their design, optimization, and integration</li> <li>Introduces the reader to the scientific aspects of bioelectrochemistry and the unique engineering problems of enzymatic fuel cells</li> <li>Offers an outlook on the practical applications of enzymatic fuel cells such as powering of microdevices, biomedical applications, and in autonomous systems</li> <li>Details future developments and emerging applications of enzymatic fuel cells</li> </ul> Enzymatic Fuel Cells is an ideal book for readers in the areas of electrochemistry, biochemistry, materials science, biosensors, biotechnology, environmental and chemical engineering, wastewater, and biology.