Temperature Dependence of Oxygen Evolution Reaction Activity in Alkaline Solution at Ni–Co Oxide Catalysts with Amorphous/Crystalline Surfaces

Abstract

The development of high-performance oxygen evolution reaction (OER) catalysts based on earth-abundant transition metal oxides as alternatives to precious metal oxides is being pursued intensively for the large-scale application of alkaline water electrolysis for hydrogen production. Active OER electrocatalysts can be designed on the basis of fundamental insights into the catalytic phenomena occurring on surfaces. In particular, the temperature dependence of OER activity as a measure of reaction energies/barriers needs to be characterized by taking into account the operating temperature (60–80 °C) of a practical water electrolyzer. In this work, we synthesized Ni–Co oxide solid solution catalysts by the flame pyrolysis method, with particular emphasis on the temperature dependence of the OER catalysis, as a way to elucidate the catalytic reactions, from both experimental and theoretical perspectives. The as-prepared catalysts structured with conductive Ni–Co alloys were heat-treated at different temperatures in the presence of O2 to regulate the crystallinity of the oxide surfaces. The OER activity has been evaluated from 20 to 80 °C in 1 M KOH, and the OER kinetic current density was found to increase with increasing temperature for all catalysts obtained. Interestingly, the Ni–Co/oxide materials with amorphous or poorly crystalline oxide surfaces showed superior activity (3–8 times higher surface-specific activity at 1.55 V vs reversible hydrogen electrode (RHE)) than their crystalline counterparts at all temperatures. The OER activation energy also decreased with decrease of the crystalline oxide phases. It was demonstrated that the catalyst with amorphous Ni–Co oxide surfaces could be readily activated to form active oxyhydroxides under alkaline OER conditions. The amorphous or disordered structure of the surface oxide with low-coordinated sites is proposed to render the surface geometry energetically favorable for the rate-determining step O + OH → OOH, which accelerates the reaction kinetics and thus improves the OER activity, as explained by density functional theory calculations.