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Exploring efficient and low-cost electrocatalysts for hydrogen evolution reaction (HER) in alkaline media is critical for developing anion exchange membrane electrolyzers. The key to a rational catalyst design is understanding the descriptors that govern the alkaline HER activity. Unfortunately, the principles that govern the alkaline HER performance remain unclear and are still under debate. By studying the alkaline HER at a series of NiCu bimetallic surfaces, where the electronic structure is modulated by the ligand effect, we demonstrate that alkaline HER activity can be correlated with either the calculated or the experimental-measured d band center (an indicator of hydrogen binding energy) via a volcano-type relationship. Such correlation indicates the descriptor role of the d band center, and this hypothesis is further supported by the evidence that combining Ni and Cu produces a variety of adsorption sites, which possess near-optimal hydrogen binding energy. Our finding broadens the applicability of d band theory to activity prediction of metal electrocatalysts and may offer an insightful understanding of alkaline HER mechanism.

Surface Composition Dependent Ligand Effect in Tuning the Activity of Nickel–Copper Bimetallic Electrocatalysts toward Hydrogen Evolution in Alkaline