High-entropy alloys have received considerable attention in the field of catalysis due to their exceptional properties. However, few studies hitherto focus on the origin of their outstanding performance and the accurate identification of active centers. Herein, we report a conceptual and experimental approach to overcome the limitations of single-element catalysts by designing a FeCoNiXRu (X: Cu, Cr, and Mn) High-entropy alloys system with various active sites that have different adsorption capacities for multiple intermediates. The electronegativity differences between mixed elements in HEA induce significant charge redistribution and create highly active Co and Ru sites with optimized energy barriers for simultaneously stabilizing OH^* and H^* intermediates, which greatly enhances the efficiency of water dissociation in alkaline conditions. This work provides an in-depth understanding of the interactions between specific active sites and intermediates, which opens up a fascinating direction for breaking scaling relation issues for multistep reactions.

To understand the mechanism of the reaction catalyzed by high-entropy-alloy (HEA) electrocatalysts, it has become increasingly crucial to investigate the chemical nature of the adsorbed intermediate species on the metal sites. Herein, we proposed a high-entropy atomic environment regulation strategy to convert inactive to active sites for electrocatalysis. Integrating the low-electronegativity Mn and high-electronegativity Cu with Fe, Co, and Ni base metals to form a FeCoNiCuMn HEA nanoparticles (NPs) would drive the inactive Cu to electron-enriched active sites through the strong local electron interaction induced by electronegativity differences, thus availably reducing the adsorption energies of the reactants, intermediates and products and accordingly enhancing the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity of HEA. The HEA achieved excellent electrocatalytic activity for both the hydrogen evolution reaction (HER) (281 mV at 100 mA cm⁻²) and the oxygen evolution reaction (OER) (386 mV at 200 mA cm⁻²) and exhibited superior cycling stability, outperforming the benchmark Pt/C and IrO₂ catalysts. This work presents breakthroughs in the design of advanced HEA electrocatalysts for complex reactions.