Enzymatic Fuel Cells From Fundamentals to Applications
, by Luckarift, Heather R.; Atanassov, Plamen B.; Johnson, Glenn R.
- ISBN: 9781118369234 | 1118369238
- Cover: Hardcover
- Copyright: 5/27/2014
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
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.
1. Introduction - Enzymatic Fuel Cells: From Fundamentals to Applications
2. Electrochemical Evaluation of Enzymatic Fuel cells and Figures of Merit
2.1 Introduction
2.2 Electrochemical Characterization
2.2.1 Open circuit measurements
2.2.2 CV
2.2.3 Electron transfer
2.2.4 Polarization curves
2.2.5 Power curves
2.2.6 EIS
2.2.7 Multi-enzyme cascades
2.2.8 RDE voltammetry
2.3 Outlook
3. Direct Bioelectrocatalysis: Oxygen Reduction for Biological Fuel cells
3.1 Introduction
3.2 Mechanistic studies of intramolecular electron transfer
3.2.1 Determining the redox potential of MCO
3.2.2 Effect of pH and inhibitors on the electrochemistry of MCO
3.3 Achieving DET of MCO by rational design
3.3.1 Surface analysis of enzyme-modified electrodes
3.3.2 Design of MCO-modified bio-cathodes based on direct bioelectrocatalysis
3.3.3 Design of MCO-modified “air-breathing” bio-cathodes
3.4 Outlook
4. Anodic Catalysts for Oxidation of Carbon-Containing Fuels
4.1 Introduction
4.2 Oxidases
4.2.1 Electron transfer mechanisms of glucose oxidase
4.3 Dehydrogenases
4.3.1 The NADH re-oxidation issue
4.3.2 Mediators for electrochemical oxidation of NADH
4.3.3 Electropolymerization of azines
4.3.4 Alcohol dehydrogenase as a model system
4.4 PQQ enzymes
4.5 Outlook
5. Anodic Bioelectrocatalysis: From Metabolic Pathways to Metabolons
5.1 Introduction
5.2 Biological fuels
5.3 Promiscuous enzymes vs. multi-enzyme cascades vs. metabolons
5.3.1 Promiscuous enzymes
5.3.2 Multi-enzyme cascades
5.3.3 Metabolons
5.4 Direct and mediated electron transfer
5.5 Fuels
5.5.1 Hydrogen
5.5.2 Ethanol
5.5.3 Methanol
5.5.4 Methane
5.5.5 Glucose
5.5.6 Sucrose
5.5.7 Trehalose
5.5.8 Fructose
5.5.9 Lactose
5.5.10 Lactate
5.5.11 Pyruvate
5.5.12 Glycerol
5.5.13 Fatty Acids
5.6 Outlook
6. Bioelectrocatalysis of Hydrogen Oxidation/Reduction by Hydrogenases
6.1 Introduction
6.2 Hydrogenases
6.3 Biological fuel cells utilizing hydrogenases: Electrocatalysis
6.4 Electrocatalysis by functional mimics of hydrogenases
6.4.1 [FeFe]-hydrogenase models
6.4.2 [NiFe]-hydrogenase models
6.4.3 Incorporation of outer coordination sphere features
6.5 Outlook
7. Protein Engineering for Enzymatic Fuel Cells
7.1 Engineering enzymes for catalysis
7.2 Engineering other properties of enzymes
7.2.1 Stability
7.2.2 Size
7.2.3 Cofactor specificity
7.3 Enzyme immobilization and self-assembly
7.3.1 Engineering for supermolecular assembly
7.4 Artificial metabolons
7.4.1 DNA-templated metabolons
7.5 Outlook
8. Purification and Characterization of Multicopper oxidases for Enzyme Electrodes
8.1 Introduction
8.2 General considerations for MCO expression and purification
8.3 MCO production and expression systems
8.4 MCO purification
8.5 Copper stability and specific considerations for MCO production
8.6 Spectroscopic monitoring and characterization of copper centers
8.7 Outlook
9. Mediated Enzyme Electrodes
9.1 Introduction
9.2 Fundamentals
9.2.1 Electron transfer overpotentials
9.2.2 Electron transfer rate
9.2.3 Enzyme kinetics
9.3 Types of mediation
9.3.1 Freely diffusing mediator in solution
9.3.2 Mediation in cross linked redox polymers
9.3.2.1 The “wired” glucose oxidase anode
9.3.3 Further redox polymer mediation
9.3.4 Mediation in other immobilized layers
9.4 Aspects of mediator design I: Mediator overpotentials
9.4.1 Considering species potentials in a methanol-oxygen BFC
9.4.2 The earliest methanol-oxidizing BFC anodes
9.4.3 A four-enzyme methanol-oxidizing anode
9.5 Aspects of mediator design II: Saturated mediator kinetics
9.5.1 An immobilized laccase cathode
9.5.2 Potential of the osmium redox polymer
9.5.3 Concentration of redox sites in the mediator film
9.6 Outlook
10. Hierarchical Material Architectures for Enzymatic Fuel Cells
10.1 Introduction
10.2 Carbon nanomaterials and the construction of the bio–nano interface
10.2.1 Carbon black nanomaterials
10.2.2 Carbon nanotubes
10.2.3 Graphene
10.2.4 CNT-decorated porous carbon architectures
10.2.5 Buckypaper
10.3 Biotemplating: The assembly of nanostructured biological–inorganic materials
10.3.1 Protein-mediated 3D biotemplating
10.4 Fabrication of hierarchically ordered 3D materials for enzyme and microbial electrodes
10.4.1 Chitosan–CNT conductive porous scaffolds
10.4.2 Polymer/carbon architectures fabricated using solid templates
10.5 Incorporating conductive polymers into bioelectrodes for fuel cell applications
10.5.1 Conductive polymer-facilitated DET between laccase and a conductive surface
10.5.2 Materials design for MFC
10.6 Outlook
11. Enzyme Immobilization for Biological Fuel Cell Applications
11.1 Introduction
11.2 Immobilization by physical methods
11.2.1 Adsorption
11.3 Entrapment as a pre- and post-immobilization strategy
11.3.2 Stabilization via encapsulation
11.3.3 Redox hydrogels
11.4 Enzyme immobilization via chemical methods
11.4.1 Covalent immobilization
11.4.2 Molecular tethering
11.4.3 Self-assembly
11.5 Orientation matters
11.6 Outlook
12. Interrogating Immobilized Enzymes in Hierarchical Structures
12.1 Introduction
12.2 Estimating the bound active (redox) enzyme
12.2.1 Modeling the performance of immobilized redox enzymes in flow-through mode to estimate the concentration of substrate at the enzyme surface
12.3 Probing the distribution of immobilized enzyme within hierarchical structures
12.4 Probing the immediate chemical microenvironments of enzymes in hierarchical structures
12.5 Enzyme aggregation in a hierarchical structure
12.6 Outlook
13. Imaging and Characterization of the Bio-Nano Interface
13.1 Introduction
13.2 Imaging the bio–nano interface
13.2.1 SEM
13.2.1.1 Backscattered electrons
13.2.1.2 Three-dimensional imaging
13.2.2 TEM
13.3 Characterizing the bio–nano interface
13.3.1 XPS
13.3.1.1 Specific considerations for analysis of enzymes using XPS
13.3.1.2 Instrumentation and experimental details for XPS of biomolecules
13.3.1.3 Elemental quantification for fingerprinting enzymes
13.3.1.4 High-resolution analysis for fingerprinting enzymes
13.3.1.5 Probing molecular interactions
13.3.1.6 Probing physical architecture of thin films using ARXPS
13.3.2 SPR
13.4 Interrogating the bio–nano interface
13.4.1 AFM
13.4.1.1 Basic principles of AFM
13.4.1.2 AFM techniques
13.4.1.3 Examples of AFM analysis and applications
13.5 Outlook
14. Scanning Electrochemical Microscopy for Biological Fuel Cell Characterization
14.1 Introduction
14.2 Theory and operation
14.3 Ultra microelectrodes
14.3.1 Approach curve method of analysis
14.4 Modes of SECM operation
14.4.1 Negative feedback mode
14.4.2 Positive feedback mode
14.4.3 Generation-collection mode
14.4.4 Induced transfer mode
14.5 SECM for BFC anodes
14.5.1 Enzyme mediated feedback imaging
14.5.1.1 Imaging glucose oxidase activity using FB mode
14.5.2 Generation-collection mode imaging
14.5.2.1 Imaging GOx using SG/TC mode
14.6 SECM for BFC cathodes
14.6.1 Tip generation-substrate collection mode
14.6.1.1 Imaging ORR by TG/SC mode
14.6.1.2 Imaging laccase by SG/TC mode
14.6.2 Redox competition mode
14.6.2.1 Imaging ORR by RC mode
14.7 Catalyst screening using SECM
14.8 SECM for membranes
14.9 Probing single enzyme molecules using SECM
14.10 Combining SECM with other techniques
14.10.1 Atomic force microscopy
14.10.2 CLSM
14.11 Outlook
15. In Situ X-ray Spectroscopy of Enzymatic Catalysis: Laccase-Catalyzed Oxygen Reduction
15.1 Introduction
15.2 Defining the enzyme/electrode interface
15.3 DET vs. MET
15.3.1 MET
15.4 The blue copper oxidases
15.4.1 Laccase
15.5 In situ XAS
15.5.1 Os L3-edge
15.5.2 uMET
15.5.3 MET
15.5.4 FEFF8.0 analysis
15.6 Proposed ORR mechanism
15.7 Outlook
16. Enzymatic Fuel Cell Design, Operation and Application
16.1 Introduction
16.2 Bio-batteries and EFCs
16.3 Components
16.3.1 Anodes
16.3.2 Cathodes
16.3.3 Separator and membrane
16.3.4 Reference electrode
16.3.5 Fuel and electrolyte
16.4 Single-cell design
16.4.1 Design of single-cell EFC compartment
16.5 Microfluidics EFC design
16.6 Stack cell design
16.6.1 Series-connected EFC stack
16.6.2 Parallel connected EFC stack
16.7 Bipolar electrodes
16.8 Air/oxygen supply
16.9 Fuel supply
16.9.1 Fuel flow through
16.9.2 Fuel flow through system
16.9.3 Fuel flow through operation and fuel waste management
16.10 Storage and shelf life
16.11 EFC operation, control, and integration with other power sources
16.11.1 Activation
16.12 EFC control
16.13 Power conditioning
16.14 Outlook
17. Miniature Enzymatic Fuel Cells
17.1 Introduction
17.2 Insertion MEFC
17.2.1 Insertion MEFC with needle anode and gas-diffusion cathode
17.2.2 Windable, replaceable enzyme electrode films
17.3 Microfluidic MEFC
17.3.1 Effects of structural design on cell performances
17.3.2 Automatic air valve system
17.3.3 SPG system
17.4 Flexible sheet MEFC
17.5 Outlook
18. Switchable Electrodes and Biological Fuel Cells
18.1 Introduction
18.2 Switchable electrodes for bioelectronic applications
18.3 Light-switchable modified electrodes based on photoisomerizable materials
18.4 Magneto-switchable electrochemical reactions controlled by magnetic species associated with electrode interfaces
18.5 Modified electrodes switchable by applied potentials resulting in electrochemical transformations at functional interfaces
18.5.1 Chemically/biochemically-switchable electrodes
18.5.2 Coupling of switchable electrodes with biomolecular computing systems
18.6 BFCs with switchable/tunable power output
18.6.1 Switchable/tunable BFCs controlled by electrical signals
18.6.2 Switchable/tunable BFC controlled by magnetic signals
18.6.3 BFCs controlled by logically processed biochemical signals
18.7 Outlook
19. Concluding Remarks and Outlook
19.1 Introduction
19.2 Primary system engineering: Design determinants
19.3 Fundamental advances in bioelectrocatalysis
19.4 Design opportunities from EFC operation
19.5 Fundamental drivers for EFC miniaturization
19.6 Commercialization of EFCs: Strategies and opportunities
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