Effects of Axial Coordination of the Metal Center on the Activity of Iron Tetraphenylporphyrin as a Nonprecious Catalyst for Oxygen Reduction

Effects of axial coordination of the metal center on oxygen reduction catalyzed by iron tetraphenylporphyrin have been studied using spectroelectrochemical and rotating ring disk electrode techniques. Among numerous ligands studied, the strongest complexation of the metal center was observed for imidazole and some substituted imidazole ligands. Around 300 mV positive shift of the oxygen reduction potential in 0.5 M H2SO4 was observed when the catalyst support (high surface area carbon Vulcan XC72) was impregnated with polyvinylimidazole. A smaller 200 mV shift of the reduction potential was recorded when graphene modified with 1-(3-aminopropyl)imidazole was used as the catalyst support instead of Vulcan. In both cases, the catalyst selectivity for four-electron reduction was also substantially improved. The effects of iron complexation on oxygen reduction kinetics and mechanism result from both a positive shift of the potential of the first porphyrin reduction and an increase of the electron density on the iron center through the so-called push effect. The observed phenomena are discussed in relation to heat-treated Fe/N/C catalysts for oxygen reduction.