Operando X-Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt-Iron (Oxy)hydroxide Electrocatalysts.
Lisa J EnmanMichaela Burke StevensMeir Haim DahanMichael R NellistMaytal Caspary TorokerShannon W BoettcherPublished in: Angewandte Chemie (International ed. in English) (2018)
Iron cations are essential for the high activity of nickel and cobalt-based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando X-ray absorption spectroscopy and density functional theory calculations are used to demonstrate partial Fe oxidation and a shortening of the Fe-O bond length during oxygen evolution on Co(Fe)Ox Hy . Cobalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate a different mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water-oxidation catalysis on Co(Fe)Ox Hy .