An electrodeposited redox polymer-laccase composite film for highly efficient four-electron oxygen reduction

Abstract

In this report, it is shown that novel thin films of Os(dcbpy)2 (dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine)-based redox polymer-laccase composite can be electrodeposited onto carbon electrodes under mild conditions. In a nutshell, the exchange of the inner-sphere Cl- of the Os(dcbpy)2Cl+/2+ complex tethered to partially quaternized poly (4-vinylpyridine) (PVP) by a pyridine ligand of a second PVP chain leads to cross-linking and deposition of the redox polymer. Laccase, which has coordinatively linkable functions of amines and histidines, is readily incorporated in the electrodeposited redox polymer. Because the reaction centers of the co-deposited laccase are electrically connected to the electrode through the deposited redox polymer, the electrodeposited film can catalyze the electroreduction of O2 at 0.58 V (vs. Ag/AgCl) - the least reducing potential for highly efficient four-electron reduction of O2 in pH 5.5 0.10 M phosphate buffer solution. Furthermore, the electroreduction of O2 is found to be O2 transport-limited when the reduction potential is poised at ≥120 mV more reducing than that of the reversible O2/H2O couple. This composite film could be an excellent candidate for uses as cathode in enzymatic biofuel cells. © 2012 Published by Elsevier B.V. All rights reserved.