Interface Metal Oxides Regulating Electronic State around Nickel Species for Efficient Alkaline Hydrogen Electrocatalysis

Abstract Heterogeneous electrocatalysis typically depends on the surface electronic states of active sites. Modulating the surface charge state of an electrocatalysts can be employed to improve performance. Among all the investigated materials, nickel (Ni)‐based catalysts are the only non‐noble‐metal‐based alternatives for both hydrogen oxidation and evolution reactions (HOR and HER) in alkaline electrolyte, while their activities should be further improved because of the unfavorable hydrogen adsorption behavior. Hereto, Ni with exceptional HOR electrocatalytic performance by changing the d‐band center by metal oxides interface coupling formed in situ is endowed. The resultant MoO₂ coupled Ni heterostructures exhibit an apparent HOR activity, even approaching to that of commercial 20% Pt/C benchmark, but with better long‐term stability in alkaline electrolyte. An exceptional HER performance is also achieved by the Ni‐MoO₂ heterostructures. The experiment results are rationalized by the theoretical calculations, which indicate that coupling MoO₂ with Ni results in the downshift of d‐band center of Ni, and thus weakens hydrogen adsorption and benefits for hydroxyl adsorption. This concept is further proved by other metal oxides (e.g., CeO₂, V₂O₃, WO₃, Cr₂O₃)‐formed Ni‐based heterostructures to engineer efficient hydrogen electrocatalysts.