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.

LanguageEnglish (US)
Pages149-155
Number of pages7
JournalJournal of Electroanalytical Chemistry
Volume626
Issue number1-2
DOIs
StatePublished - Feb 15 2009

Profile

Osmium
Laccase
Polymers
Cathodes
Oxygen
Current density
Electrodes
Enzyme electrodes
Rotating disks
Citric Acid
Oxidation-Reduction
Charge transfer
Buffers
Carbon
Mass transfer
Kinetics
Water
Composite materials

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

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