Abstract
Incorporation of metalloporphyrins into polypyrrole (PPy) film was achieved either by electropolymerization of pyrrole in the presence of metal-tetra(sulfonatophenyl)porphyrin anion (MTSPP, M=Co, Fe) or by metalizing hydrogenated tetra(4-sulfonatophenyl)porphyrin anion (H2TSPP) doped into PPy through ion-exchange. Electrochemical reduction of oxygen on the PPy doped with metallo porphyrin (PPy-MTSPP) was studied in acidic and basic solutions. Oxygen reduction on PPy-MTSPP electrodes appeared to proceed through a 4-electron pathway as well as a 2-electron path. In acidic solutions, the overpotential for O2 reduction on PPy-CoTSPP electrode was smaller than that on gold by about 0.2 V. In basic solutions the overpotential of the PPy-CoTSPP electrode in the activation range was close to those of Au and Pt. The limiting current was close to that of Au. However, polypyrrole doped with cobalt-tetra(sulfonatophenyl)porphyrin anion (PPy-CoTSPP) or with iron-tetra(sulfonatophenyl)porphyrin anion (PPy-FeTSPP) was found to have limited potential windows at high temperatures (above 50 ℃), and hence the electrode could not be held at the oxygen reduction potentials in basic solutions (pH 13) without degradation of the polymer.