Manipulating the Water Dissociation Electrocatalytic Sites of Bimetallic Nickel-Based Alloys for Highly Efficient Alkaline Hydrogen Evolution

Transition-metal alloys are currently drawing increasing attention as promising electrocatalysts for the alkaline hydrogen evolution reaction (HER). However, traditional density-functional-theory-derived d-band theory fails to describe the hydrogen adsorption energy (ΔG_H) on hollow sites. Herein, by studying the ΔG_H for a series of Ni−M (M=Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, W) bimetallic alloys, an improved d-band center was provided and a potential NiCu electrocatalyst with a near-optimal ΔG_H was discovered. Moreover, oxygen atoms were introduced into Ni−M (O−NiM) to balance the adsorption/desorption of hydroxyl species. The tailored electrocatalytic sites for water dissociation can synergistically accelerate the multi-step alkaline HER. The prepared O−NiCu shows the optimum HER activity with a low overpotential of 23 mV at 10 mA cm⁻². This work not only broadens the applicability of d-band theory, but also provides crucial understanding for designing efficient HER electrocatalysts.