Abstract
Electrolytic reduction of oxygen in neutral and acidic solutions has been studied at polypyrrole film electrodes doped with metalloporphyrins (metal complexes of meso-tetrakis (4-sulfonatophenyl)porphyrin [MTPPS 4, M=CO, Fe, Mn]. Redox behavior of the metalloporphyrins, which are free in solutions and are immobilised in polypyrroles, has been clarified by means of optically transparent electrodes. It is observed that the catalytic activity for O 2 reduction at the porphyrin-doped polypyrroles (MPPP) in the neutral solution is controlled by the redox cycle of metal ion or the mediated charge transfer, but not in the acidic solution. An experiment on CoPPP in the acidic solution reveals that two O 2 reduction mechanisms which are independent and dependent on the mediated charge transfer are present depending on potential. It is found that a polypyrrole film electrode doped with H 2 TPPS 4 containing no metal ion can be metallized by immersing the electrode in a heated aqueous solution of cobalt(II) acetate.
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