Augmented Electrochemical Oxygen Evolution by d–p Orbital Electron Coupling

Abstract While high‐entropy alloys, high‐entropy oxides, and high‐entropy hydroxides, are advanced as a novel frontier in electrocatalytic oxygen evolution, their inherent activity deficiency poses a major challenge. To achieve the unlimited goal to tailor the structure–activity relationship in multicomponent systems, entropy‐driven composition engineering presents substantial potential, by fabricating high‐entropy anion‐regulated transition metal compounds as sophisticated oxygen evolution reaction electrocatalysts. Herein, a versatile 2D high‐entropy metal phosphorus trisulfide is developed as a promising and adjustable platform. Leveraging the multiple electron couplings and d–p orbital hybridizations induced by the cocktail effect, the exceptional oxygen evolution catalytic activity is disclosed upon van der Waals material (MnFeCoNiZn)PS₃, exhibiting an impressively low overpotential of 240 mV at a current density of 10 mA cm⁻², a minimal Tafel slope of 32 mV dec⁻¹, and negligible degradation under varying current densities for over 96 h. Density functional theory calculations further offer insights into the correlation between orbital hybridization and catalytic performance within high‐entropy systems, underscoring the contribution of active phosphorus centers on the substrate to performance enhancements. Moreover, by achieving electron redistribution to optimize the electron coordination environment, this work presents an effective strategy for advanced catalysts in energy‐related applications.