Anionic Engineering of ReS₂‐Re₂O₇‐Ni(OH)₂/NF Heterostructure for Enhanced Alkaline Hydrogen Evolution

Abstract Rhenium disulfide (ReS 2 ) has garnered increasing attention in the field of electrocatalysis as a highly promising catalyst for hydrogen evolution reaction (HER), whereas regulating the in‐plane catalytic activity and electrical conductivity of ReS 2 remains a challenge. Herein, self‐supported ReS 2 ‐Re 2 O 7 ‐Ni(OH) 2 nanoelectrodes with high conductivity were grown on nickel foam through a mild electrodeposition method combined with an anion engineering strategy. Density functional theory (DFT) calculations reveal the moderate adsorption of the reaction intermediate H on the Re site, while current density simulations indicate that the ReS 2 ‐Re 2 O 7 ‐Ni(OH) 2 /NF material exhibits higher conductivity and a uniform current density distribution. As a consequence, the optimized ReS 2 ‐Re 2 O 7 ‐Ni(OH) 2 /NF material demonstrates excellent HER activity and long‐term stability in alkaline media (1 M KOH), achieving a low overpotential of 83 mV versus RHE at a current density of 10 mA cm −2 , a Tafel slope of 77 mV dec −1 , and maintains long‐term stability of 72 h. The strategy of anion engineering offers a new perspective in the design and development of highly efficient electrocatalysts for energy conversion and storage applications.