D‐Band Modulation by Elements Synergistic Design for High‐Performance Zinc Air Batteries

ABSTRACT High‐entropy nitrides (HENs) are promising electrocatalysts for water oxidation and hydrogen production owing to their exceptional physicochemical properties. However, the modulation of the d‐band center and electronic configuration, driven by elemental synergy, is crucial for developing high‐performance HENs for electrochemical applications. Herein, ultrafine (∼10 nm) HEN nanoparticles anchored on N‐doped graphitic carbon were synthesized via a salt‐template assisted method, achieving uniform elemental distribution. The optimized catalyst exhibits an onset potential of 0.978 V for the oxygen reduction reaction and an overpotential of 291.8 mV at 100 mA cm ⁻² for the oxygen evolution reaction. The corresponding zinc‐air battery demonstrates a high open‐circuit voltage of 1.529 V and stability over 450 cycles. Density functional theory suggests that synergistic modulation of elements optimizes the electronic structure and d‐band center of HENs, enhancing adsorption and desorption of ^* OH intermediates and reducing the free energy barrier during the reaction process. Partial density of states analysis reveals that W element modulates the electronic environment of the other four elements, inducing electronic reconstruction and a shift of the d‐band center of the metal active sites. This work elucidates the electrocatalytic mechanism of elemental interactions in HENs and provides a guideline for designing advanced high‐entropy materials.