In-Situ Formed Hydroxide Accelerating Water Dissociation Kinetics on Co₃N for Hydrogen Production in Alkaline Solution

Sluggish water dissociation kinetics on nonprecious metal electrocatalysts limits the development of economical hydrogen production from water-alkali electrolyzers. Here, using Co₃N electrocatalyst as a prototype, we find that during water splitting in alkaline electrolyte a cobalt-containing hydroxide formed on the surface of Co₃N, which greatly decreased the activation energy of water dissociation (Volmer step, a main rate-determining step for water splitting in alkaline electrolytes). Combining the cobalt ion poisoning test and theoretical calculations, the efficient hydrogen production on Co₃N electrocatalysts would benefit from favorable water dissociation on in-situ formed cobalt-containing hydroxide and low hydrogen production barrier on the nitrogen sites of Co₃N. As a result, the Co₃N catalyst exhibits a low water-splitting activation energy (26.57 kJ mol^-1) that approaches the value of platinum electrodes (11.69 kJ mol^-1). Our findings offer new insight into understanding the catalytic mechanism of nitride electrocatalysts, thus contributing to the development of economical hydrogen production in alkaline electrolytes.