Electronic redistribution over the active sites of NiWO4-NiO induces collegial enhancement in hydrogen evolution reaction in alkaline medium.

The activity-enhancement of a new-generation catalyst focuses on the collegial approach among specific solids which exploit the mutual coactions of these materials for HER applications. Strategic manipulation of these solid interfaces typically reveals unique electronic states different from their pure phases, thus, providing a potential passage to create catalysts with excellent activity and stability. Herein, the formation of the NiWO4-NiO interface has been designed and synthesized via a three-step method. This strategy enhances the chance of the formation of abundant heterointerfaces due to the fine distribution of NiWO4 nanoparticles over Ni(OH)2 sheets. NiWO4-NiO has superior HER activity in an alkaline (1 M KOH) electrolyte with modest overpotentials of 68 mV at 10 mA cm-2 current density. The catalyst is highly stable in an alkaline medium and negligible change was observed in the current density even after 100 h of continuous operation. This study explores a unique method for high-performance hydrogen generation by constructing transition metal-oxides heterojunction. The XPS studies reveal an electronic redistribution driven by charge transfer through the NiWO4-NiO interface. The density functional theory (DFT) calculations show that the NiWO4-NiO exhibits a Pt-like activity with the hydrogen Gibbs free energy (ΔGH*) value of 0.06 eV compared to the Pt(ΔGH* = -0.02 eV).