Catalysts for the oxygen reduction from heat-treated iron(III) tetramethoxyphenylporphyrin chloride:: Structure and stability of active sites

Structure and stability of an iron-based catalyst for the oxygen reduction reaction, prepared by heat treatment of carbon-supported iron(III) tetramethoxyphenylporphyrin chloride (FeTMPP-Cl), were investigated. The oxygen reduction in acid electrolyte was examined with the rotating (ring) disk electrode. The measurements confirmed that H2O2 is generated as a byproduct of the oxygen reduction. The structural elucidation of the catalyst showed that the porphyrin decomposes during heat treatment. Nitrogen atoms of the heat-treated porphyrin become bonded at the edge of graphene layers as pyridine- and pyrrole-type nitrogen. Two Fe3+ components as well as metallic, carbidic and oxidic iron were detected by Mossbauer spectroscopy. An electrochemical longevity test and two degradation experiments with sulfuric acid and H2O2 showed that H2O2 causes the degradation of active sites. A 6-fold coordinated Fe3+ compound seems to be responsible for the catalytic activity. Only 8% of the primary iron content is present in the active iron component.