A Density Functional + U Assessment of Oxygen Evolution Reaction Mechanisms on β-NiOOH

NiOx has long been studied both as a battery cathode material and electrocatalyst for the oxygen evolution reaction (OER). Numerous investigations have demonstrated that Fe-doped nickel oxyhydroxide (NiOOH) is one of the most active OER catalysts in alkaline media. Despite extensive research, however, many unanswered questions pertaining to the OER mechanism on this material remain. Here, using density functional theory + U calculations, we compare several surfaces of β-NiOOH studied for the OER and determine that unlike some earlier models selected, the (001) surface is the most stable surface under electrochemical conditions. We then examine several magnetic states of this material and predict that, unlike bulk β-NiOOH, (001)-β-NiOOH manifests a slight preference to be ferromagnetic. We then use the resulting structural model to compare in detail four commonly proposed OER mechanisms. In addition to excluding a proposed mechanism involving hydrogen peroxide formation, we identify multiple binuclear mech...