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Three-Dimensional Sulfite Oxidase Bioanodes Based on Graphene Functionalized Carbon Paper for Sulfite/O2 Biofuel Cells
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    Three-Dimensional Sulfite Oxidase Bioanodes Based on Graphene Functionalized Carbon Paper for Sulfite/O2 Biofuel Cells
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    ACS Catalysis

    Cite this: ACS Catal. 2019, 9, 7, 6543–6554
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    https://doi.org/10.1021/acscatal.9b01715
    Published June 11, 2019
    Copyright © 2019 American Chemical Society

    Abstract

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    We have developed a three-dimensional (3D) graphene electrode suitable for the immobilization of human sulfite oxidase (hSO), which catalyzes the electrochemical oxidation of sulfite via direct electron transfer (DET). The electrode is fabricated by drop-casting graphene-polyethylenimine (G-P) composites on carbon papers (CPs) precoated with graphene oxide (GO). The negatively charged hSO can be adsorbed electrostatically on the positively charged matrix (G-P) on CP electrodes coated with GO (CPG), with a proper orientation for accelerated DET. Notably, further electrochemical reduction of G-P on CPG electrodes leads to a 9-fold increase of the saturation catalytic current density (jm) for sulfite oxidation reaching 24.4 ± 0.3 μA cm–2, the highest value among reported DET-based hSO bioelectrodes. The increased electron transfer rate plays a dominating role in the enhancement of direct enzymatic current because of the improved electric contact of hSO with the electrode. The optimized hSO bioelectrode shows a significant catalytic rate (kcat: 25.6 ± 0.3 s–1) and efficiency (kcat/Km: 0.231 ± 0.003 s–1 μM–1) compared to the reported hSO bioelectrodes. The assembly of the hSO bioanode and a commercial platinum biocathode allows the construction of sulfite/O2 enzymatic biofuel cells (EBFCs) with flowing fuels. The optimized EBFC displays an open-circuit voltage (OCV) of 0.64 ± 0.01 V and a maximum power density of 61 ± 6 μW cm–2 (122 ± 12 mW m–3) at 30 °C, which exceeds the best reported value by more than 6 times.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.9b01715.

    • Additional data and figures including preparation of hSO bioelectrodes, EBFC assembly, AFM image, XPS and UV–vis spectra, and electrochemical data, summary of relative peak area percentage of carbon bindings, ζ potentials, key voltammetry parameters, EIS fitting parameters, ECSAs, comparison of ECSA and Rct, bioelectrode activity assay, and enzyme kinetic parameters (PDF)

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    ACS Catalysis

    Cite this: ACS Catal. 2019, 9, 7, 6543–6554
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.9b01715
    Published June 11, 2019
    Copyright © 2019 American Chemical Society

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