DFT study of the oxygen reduction reaction on iron, cobalt and manganese macrocycle active sites

The best performing non-precious metal based catalysts for polymer electrolyte membrane fuel cells are manufactured by incorporation of nitrogen into a carbon structure in the presence of iron and cobalt. Herein, density functional theory (DFT) calculations have been performed to investigate the oxygen reduction reaction on catalyst active sites modelled as transition metal macrocycles with iron, cobalt or manganese central atoms. The effects of the transition metal and macrocycle structure have been investigated. The structure of the most promising active sites has been proposed, and the detailed potential energy profiles of the oxygen reduction reaction have been obtained over the active sites, including all intermediate steps with corresponding activation barriers. The efficiency of the active sites depends primarily on the transition metal nature, and the central iron atom accounts for the higher catalytic activity than cobalt and manganese. The central manganese atom can favour the two-electron oxygen reduction pathway and thus yielding hydrogen peroxide.