Influence of Electrolyte Cations on Ni(Fe)OOH Catalyzed Oxygen Evolution Reaction

Iron-doped, nickel oxyhydroxide (Ni(Fe)OOH) is one of the best catalysts for the oxygen evolution reaction (OER) under alkaline conditions. Due to Ni(Fe)OOH's layered structure, electrolyte species are able to easily intercalate between the octahedrally coordinated sheets. Electrolyte cations have long been considered inert spectator ions during electrocatalysis, but electrolytes that penetrate into the catalyst may play a major role in the reaction process. In a joint theoretical and experimental study, we report the role of electrolyte counterions (K+, Na+, Mg2+, and Ca2+) on Ni(Fe)OOH catalytic activity in alkaline media. We show that electrolytes containing alkali metal cations (Na+ and K+) yield dramatically lower overpotentials than those with alkaline earth cations (Mg2+ and Ca2+). K+ and Na+ lower the overpotential because they have an optimal acidity and size that allows them to not bind too strongly or alter the stability of reaction intermediates. These two features required for intercalated cation species provide insight into selecting appropriate electrolytes for layered catalyst materials, and enable understanding the role(s) of electrolytes in the OER mechanism.