Enzymatic Fuel Cells From Fundamentals to Applications

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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