Biocathodes for Dioxygen Reduction in Biofuel Cells

Bilewicz, Renata; Opałło, Marcin

doi:10.1002/9780470630693.ch5

Cited by 11 publications

(12 citation statements)

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“…1, left part). BOx has been widely used for a long time in clinical analysis [30,31] and biofuel cells [32][33][34][35][36], but the crystal structure was published only recently [37,38]. It is a highly similar to structures of other MCO and BOx contains a full complement of four copper ions per monomer, located in domains 1 and 3 [37,38].…”

Section: Introductionmentioning

confidence: 85%

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On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

et al. 2012

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The catalytic cycle of multicopper oxidases (MCOs) involves intramolecular electron transfer (IET) from the Cu‐T1 copper ion, which is the primary site of the one‐electron oxidations of the substrate, to the trinuclear copper cluster (TNC), which is the site of the four‐electron reduction of dioxygen to water. In this study we report a detailed characterization of the kinetic and electrochemical properties of bilirubin oxidase (BOx) – a member of the MCO family. The experimental results strongly indicate that under certain conditions, e.g. in alkaline solutions, the IET can be the rate‐limiting step in the BOx catalytic cycle. The data also suggest that one of the catalytically relevant intermediates (most likely characterized by an intermediate oxidation state of the TNC) formed during the catalytic cycle of BOx has a redox potential close to 0.4 V, indicating an uphill IET process from the T1 copper site (0.7 V) to the Cu‐T23. These suggestions are supported by calculations of the IET rate, based on the experimentally observed Gibbs free energy change and theoretical estimates of reorganization energy obtained by combined quantum and molecular mechanical (QM/MM) calculations.

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Section: Introductionmentioning

confidence: 85%

“…[32][33][34][35][36]), as well as in homogeneous catalysis under certain conditions, e.g. at pH 7 and higher, the IET process might be the rate-limiting step determining the ultimate efficiency of BOx-based biocatalysis.…”

Section: Discussionmentioning

confidence: 99%

On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

et al. 2012

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“…[5][6][7] To improve this technology, much research has been focused on engineering and modifying the cathode half of these biofuel cells. [8][9][10][11][12][13][14][15][16][17][18] One such engineered bioelectrode system, previously developed by our group, employs anthracene modified multi-walled carbon nanotubes (anth-MWCNTs) for docking of the oxidoreductase enzyme laccase to the current collector. This biocathode uses anthracene covalently modified to the ends of the multi-walled carbon nanotubes (MWCNTs) in order to favorably orient the laccase enzyme to the ends of the carbon nanotubes, since laccase has a hydrophobic binding site for anthracene and the aromatic structure allows for improved conductivity between the active site and the carbon surface.…”

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confidence: 99%

Operational Stability Assays for Bioelectrodes for Biofuel Cells: Effect of Immobilization Matrix on Laccase Biocathode Stability

Shrier

Giroud

Rasmussen

2014

J. Electrochem. Soc.

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One of the main issues of enzymatic biofuel cells is the need to develop stable bioelectrodes. However, there is no standard method to study bioelectrode stability. In this study, laccase and anthracene modified multiwall carbon nanotubes (anth-MWCNTs) were used in conjunction with different immobilization polymers in order to increase the stability of the biocathodes. A series of stability assays were used to understand the operational stability of the biocathode in a biofuel cell environment. The immobilization matrices used in this study were tetrabutyl ammonium bromide modified Nafion (TBAB modified Nafion), octyl modified linear polyethylenimine (C 8 -LPEI), and vapor deposited tetramethyl orthosilicate (TMOS) gels. The decrease in activity of the galvanostatic and potentiostatic measurements over a 24 hour period of the TBAB modified Nafion were 4.0 ± 0.6% and 4.1 ± 0.4%; C 8 -LPEI were 0.7 ± 0.1% and 9.6 ± 0.5%; and TMOS were 4.1 ± 0.1% and 10 ± 2.0%, respectively. This data show that potentiostatic measurements provide a harsher environment for the enzyme and result in lower stability, as well as showing that the TBAB modified Nafion offers a more stabilizing immobilization strategy compared to the C 8 -LPEI or TMOS matrices. The increasing interest in producing electrical energy from renewable resources has caused the field of biofuel cells to flourish. Enzymatic biofuel cell systems are capable of producing energy from renewable fuels. Basically, enzymatic biofuel cells (EBFC) generate electricity from the oxidation of the fuel at the anode and the reduction of the oxidant at the cathode using biological catalysts (enzymes) instead of traditional metal catalysts. More detailed descriptions of such biofuel cells can be found in reviews that discuss the fundamental concepts of this technology.1,2 Applications of EBFCs range from energy sources for small electronic devices, 3 self-powered sensors 4 and more recently as implantable power sources. [5][6][7] To improve this technology, much research has been focused on engineering and modifying the cathode half of these biofuel cells. [8][9][10][11][12][13][14][15][16][17][18] One such engineered bioelectrode system, previously developed by our group, employs anthracene modified multi-walled carbon nanotubes (anth-MWCNTs) for docking of the oxidoreductase enzyme laccase to the current collector. This biocathode uses anthracene covalently modified to the ends of the multi-walled carbon nanotubes (MWCNTs) in order to favorably orient the laccase enzyme to the ends of the carbon nanotubes, since laccase has a hydrophobic binding site for anthracene and the aromatic structure allows for improved conductivity between the active site and the carbon surface. The steric orientation provides increased catalytic reduction of oxygen to water and favorable distances such that the laccase performs direct electron transfer (DET). 8In biofuel cells, DET occurs through the enzyme's ability to oxidize or reduce a substrate while transferring the necessary electrons to or fro...

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“…superoxides or peroxides [8][9][10][11][12][13][14]. The difficulty with these redox enzyme applications is that usually an electron mediator is needed to allow electron transfer between the electrode and the active site of the enzyme [15][16][17][18]. Mediators may lead to unwanted reactions or leach to the solution, and if coimmobilized with the enzyme, they may not be sufficiently active anymore.…”

Section: Introductionmentioning

confidence: 99%

Nanostructuring carbon supports for optimal electrode performance in biofuel cells and hybrid fuel cells

Majdecka

Bilewicz

2015

J Solid State Electrochem

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The efficiencies of dioxygen reduction on common carbonaceous materials were compared using voltammetry and fuel cell measurements. Carbon paper (CP), carbon fibre (CF) or carbon cloth (CC) conducting supports were covered under water pump pressure with multiwalled carbon nanotubes (MWCNTs) to increase the working surface of the electrode, improve connectivity with enzyme molecules and provide direct electron transfer. Laccase was the biocathode catalyst catalyzing 4-electron reduction of oxygen to water on the nanostructured electrode. CP carbon paper was selected as the favourable electrode substrate, since it provided best durability holding firmly the carbon nanotubes together with the enzyme at the electrode surface. Zinc disc or fructose dehydrogenase was used as anode in the hybrid fuel cell and biofuel cell, respectively. The characteristics under externally applied resistances and potential-time dependencies under flowing solution conditions were evaluated. The hybrid fuel cell based on Zn anode and CP supported laccase cathode gave the best results in terms of power and open circuit potential (OCP). The full biofuel cell based on laccase and fructose dehydrogenase shows lower OCP but the power-time dependencies were similar to those of the hybrid biofuel cell. The nanostructured surfaces show good supercapacitor properties due to the presence of carbon nanotubes at the electrode surface. The fuel cells undergo self-charging/discharging and, therefore, can be conveniently employed in pulsed-work regime to power external devices.

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Biocathodes for Dioxygen Reduction in Biofuel Cells

Cited by 11 publications

References 250 publications

On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

On the Possibility of Uphill Intramolecular Electron Transfer in Multicopper Oxidases: Electrochemical and Quantum Chemical Study of Bilirubin Oxidase

Operational Stability Assays for Bioelectrodes for Biofuel Cells: Effect of Immobilization Matrix on Laccase Biocathode Stability

Nanostructuring carbon supports for optimal electrode performance in biofuel cells and hybrid fuel cells

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