title: Use of 'split waves' for the measurement of electrocatalytic kinetics: methyl viologen mediated oxygen reduction on a boron-doped diamond electrode.
abstract: The mediated reduction of oxygen via the reduced form of methyl viologen is studied voltammetrically. The investigation is facilitated through the use of a boron-doped diamond electrode, allowing the catalytic response to be clearly delineated from that of the direct oxygen reduction process at the electrode surface. From simulation a high homogeneous electron transfer rate (6 × 10(9) M(-1) s(-1)) is found for the one-electron reduction of oxygen to superoxide. This value is in close agreement with that found using non-electrochemical methods and is significantly higher than the values previously reported in electrochemical studies. In the latter case it is demonstrated that the underestimation of the electron transfer rate arises due to oversimplification of the reaction mechanism.
authors.affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ, UK.
authors.forename: Qianqi
authors.initials: Q
authors.lastname: Lin
authors.forename: Qian
authors.initials: Q
authors.lastname: Li
authors.forename: Christopher
authors.initials: C
authors.lastname: Batchelor-McAuley
authors.forename: Richard G
authors.initials: RG
authors.lastname: Compton
mesh_terms: D001895:Boron / Q000737:chemistry*; D002384:Catalysis; D055664:Electrochemical Techniques; D004566:Electrodes; D007700:Kinetics; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010269:Paraquat / Q000737:chemistry*
chemical_list: D001895:Boron; D010269:Paraquat; D010100:Oxygen