A Strategy Integrating “Electronic Modulation–Defect Engineering–Interfacial Water Reconstruction” for Designing High-Efficiency Hydrogen Evolution Reaction Electrocatalysts

Developing highly active and cost-effective electrocatalysts to enhance the sluggish kinetics of water dissociation is essential for hydrogen production through anion exchange membrane (AEM) water electrolysis. Guided by density functional theory simulations, a strategy integrating “electronic modulation–defect engineering–interfacial water reconstruction” was proposed. As a proof-of-concept, F-doped/P-vacancy-rich CoP with a dandelion-like structure grown on carbon paper (F-CoPv/CP) was synthesized. As shown by combined ab initio molecular dynamics simulations and X-ray absorption fine structure spectroscopy, F restructures the interfacial water network and weakens O–H bonds via modulating the electronic structure, while P vacancies expose undercoordinated high-activity Co sites and boost hydrogen desorption. Notably, F-CoPv/CP shows superior hydrogen evolution reaction (HER) activity (η₁₀₀ = 79 mV) and a long life (over 600 h at 500 mA cm^–2). The AEM electrolyzer employing F-CoPv||NiFeO_x requires only a low voltage of 2.098 V at 1000 mA cm^–2 at 60 °C. This synergistic design provides novel perspectives for designing high-efficiency HER catalysts.