Vanadium‐Driven Electron Aggregation Effect for Enhancing pH‐Universal Hydrogen Evolution in Seawater

Abstract The design of efficient, durable, and corrosion‐resistant ruthenium‐based electrocatalysts for pH‐universal hydrogen evolution reaction (HER) is of great significance for seawater electrolysis. Herein, an electron aggregation strategy is proposed to regulate the electronic structure of Ru via V doping (V‐Ru/KB). Density functional theory (DFT) calculations reveal that the incorporation of V induces an electron aggregation effect, whereby electrons are transferred from Ru to V atoms. This electron redistribution reduces the electron density on Ru, thereby weakening the adsorption strength toward hydrogen intermediates and optimizing the hydrogen adsorption free energy (ΔG H* ), which collectively promotes HER kinetics. Furthermore, the V‐Ru orbital coupling causes a downward shift of the Ru d‐band center, weakening Cl − adsorption and improving long‐term stability under seawater conditions. As a result, V‐Ru/KB exhibits a low overpotential for HER in 1.0 m KOH + seawater (η 10 = 30 mV), 0.5 m H 2 SO 4 + seawater (η 10 = 35 mV), and pure seawater (η 10 = 267 mV), along with excellent durability. This study offers a promising strategy for the development of efficient and robust electrocatalysts for practical seawater electrolysis.