Journal of Electrochemical Science and Technology

The Korean Electrochemical Society (한국전기화학회)
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Methyl Viologen Mediated Oxygen Reduction in Ethanol Solvent: the Electrocatalytic Reactivity of the Radical Cation

  • Lin, Qianqi (Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University) ;
  • Li, Qian (Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University) ;
  • Batchelor-McAuley, Christopher (Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University) ;
  • Compton, Richard G. (Department of Chemistry, Physical and Theoretical Chemistry Laboratory, Oxford University)
  • Received : 2013.06.07
  • Accepted : 2013.06.17
  • Published : 2013.06.30
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Abstract

The study of methyl viologen ($MV^{2+}$) mediated oxygen reduction in electrolytic ethanol media possesses potential application in the electrochemical synthesis of hydrogen peroxide mainly due to the advantages of the much increased solubility of molecular oxygen ($O_2$) and high degree of reversibility of $MV^{2+/{\bullet}+}$ redox couple. The diffusion coefficients of both $MV^{2+}$ and $O_2$ were investigated via electrochemical techniques. For the first time, $MV^{2+}$ mediated $O_2$ reduction in electrolytic ethanol solution has been proved to be feasible on both boron-doped diamond and micro-carbon disc electrodes. The electrocatalytic response is demonstrated to be due to the radical cation, $MV^{{\bullet}+}$. The homogeneous electron transfer step is suggested to be the rate determining step with a rate constant of $(1{\pm}0.1){\times}10^5M^{-1}s^{-1}$. With the aid of a simulation program describing the EC' mechanism, by increasing the concentration ratio of $MV^{2+}$ to $O_2$ electrochemical catalysis can be switched from a partial to a 'total catalysis' regime.

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