Effect of redox polymer synthesis on the performance of a mediated laccase oxygen cathode

Joshua W. Gallaway, Scott A. Calabrese Barton

    Research output: Contribution to journalArticle

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    Abstract

    Water-soluble, crosslinkable redox polymers are synthesized from poly(N-vinylimidazole) and an osmium complex, with variation in the concentration and reactant mole ratio of these precursor materials. Higher reactant concentration results in increased osmium loading on the redox polymer backbone, with products produced having a range of 19-23 imidazole repeat units per pendant osmium redox site. Performance of oxygen-reducing enzyme electrodes prepared from the redox polymers and laccase from Trametes versicolor on vitreous carbon rotating disks displays a high dependence on osmium mass fraction, with observed current densities varying by nearly a factor of two over the range osmium fractions studied. The highest-performing electrode produces a current density of 2.1 ± 0.2 mA/cm2 at 0.65 V and 900 rpm in 0.1 M pH 4 citrate buffer at 40 °C, which to our knowledge is greater than any previous analogous electrode. The gain in catalytic performance with osmium mass fraction is attributed to both increased charge transport and mediation kinetics. When scaled to high surface area composite electrodes 13 ± 0.8 mA/cm2 is produced at a rotation rate of 900 rpm, and current densities exceed 20 mA/cm2 when mass transport limitation is further eliminated.

    Original languageEnglish (US)
    Pages (from-to)149-155
    Number of pages7
    JournalJournal of Electroanalytical Chemistry
    Volume626
    Issue number1-2
    DOIs
    StatePublished - Feb 15 2009

    Profile

    Osmium
    Oxidation-Reduction
    Polymers
    Current density
    Electrodes
    Contraceptives, Oral, Combined
    Autoradiography
    Oxygen
    Enzyme electrodes
    Rotating disks
    Charge transfer
    Cathodes
    Mass transfer
    Kinetics
    Carbon
    Composite materials
    Water
    Edema Disease of Swine
    Feline Panleukopenia
    Coumestrol

    Keywords

    • Biofuel cell
    • Enzyme electrode
    • Laccase
    • Mediated electron transfer
    • Oxygen reduction
    • Redox polymer

    ASJC Scopus subject areas

    • Chemical Engineering(all)
    • Analytical Chemistry
    • Electrochemistry

    Cite this

    Effect of redox polymer synthesis on the performance of a mediated laccase oxygen cathode. / Gallaway, Joshua W.; Calabrese Barton, Scott A.

    In: Journal of Electroanalytical Chemistry, Vol. 626, No. 1-2, 15.02.2009, p. 149-155.

    Research output: Contribution to journalArticle

    Gallaway, Joshua W.; Calabrese Barton, Scott A. / Effect of redox polymer synthesis on the performance of a mediated laccase oxygen cathode.

    In: Journal of Electroanalytical Chemistry, Vol. 626, No. 1-2, 15.02.2009, p. 149-155.

    Research output: Contribution to journalArticle

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