Abstract
Conducting poly(3,4-ethylenedioxythiophene) (PEDT) films with metalloporphyrins incorporated as the counter ions were prepared by electropolymerization of the monomer in the presence of metal-tetra(sulfonatophenyl) porphyrin anions. Cathodic reduction of oxygen on the resulting conducting polymer films was studied. The overpotential for O2 reduction on electrodes with cobalt-porphyrin complex was significantly smaller in acidic solutions than on gold. In basic solutions, the overpotential at low current densities was close to those on platinum and gold. Polymer electrode with Co-complex yielded higher limiting currents than with Fe-complex, although the Co-complex polymer electrode was a poorer electrocatalyst for O2 reduction in the activation range of potential than the Fe counterpart. From the rotating ring-disk electrode experiments, oxygen reduction was shown to proceed through either a 4-electron pathway or a 2-electron pathway. In contrast to the polypyr-role-based electrodes, the PEDT-based metalloporphyrin electrodes were stable with wider potential windows, including the oxygen reduction potential. Their electrocatalytic properties were maintained at temperatures up to 80℃ in KOH solutions.