Electrocatalytic Dioxygen Reduction by Carbon Electrodes Noncovalently Modified with Iron Porphyrin Complexes: Enhancements from a Single Proton Relay

Oxygen reduction in acidic aqueous solution mediated by a series of asymmetric iron (III)‐tetra(aryl)porphyrins adsorbed to basal‐ and edge‐ plane graphite electrodes is investigated. The asymmetric iron porphyrin systems bear phenyl groups at three meso positions and either a 2‐pyridyl, a 2‐benzoic acid, or a 2‐hydroxyphenyl group at the remaining meso position. The presence of the three unmodified phenyl groups makes the compounds insoluble in water, enabling catalyst retention during electrochemical experiments. Resonance Raman data demonstrate that catalyst layers are maintained, but can undergo modification after prolonged catalysis in the presence of O2. The introduction of a single proton relay group at the fourth meso position makes the asymmetric iron porphyrins markedly more robust catalysts; these molecules support higher sustained current densities than the parent iron tetraphenylporphyrin. Iron porphyrins bearing a 2‐pyridyl group are the most active catalysts and operate at stable current densities ≥1 mA cm−2 for over 5 h. Comparative analysis of the catalysts with different proton relays also is reported. Relay saying something: Iron porphyrin catalysts that incorporate hydrophobic aromatic groups and a proton relay absorb strongly to carbon electrodes and promote catalytic reduction of O2. The introduction of a single proton relay group at one meso position makes the asymmetric iron porphyrins markedly more robust catalysts than the parent iron tetraphenylporphyrin (see figure; BPG=basal plane graphite, EPG=edge plane pyrolytic graphite).