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

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.