Zn-induced interatomic electron transfer channels in heterostructured phosphides for robust bifunctional oxygen catalysis

Developing highly efficient and stable non-precious-metal bifunctional oxygen electrocatalysts remains a primary bottleneck for the widespread application of rechargeable zinc-air batteries (RZABs). While transition-metal phosphides (TMPs) are promising candidates, their efficacy is fundamentally constrained by the mutually exclusive adsorption-energy requirements of oxygen intermediates during the oxygen reduction and evolution reactions (ORR/OER). Herein, an innovative Zn-induced electron-bridge strategy is proposed to construct strongly coupled heterointerfaces with atomic-scale precision. In this design, Zn species act dually as structure-directing agents and electronic modulators. Comprehensive experimental and theoretical analyses demonstrate that Zn incorporation strategically optimizes the d -band centers of the Fe/Ni active sites, alleviating the excessively strong adsorption of oxygenated intermediates. Furthermore, it establishes interatomic cross-interfacial electron-transfer channels that synergistically accelerate reaction kinetics. Consequently, the engineered Zn-FeNiP nanocomposite, confined within a three-dimensional (3D) N, P-codoped carbon matrix (Zn-FeNiP@3DNPC), delivers outstanding bifunctional performance with a narrow potential gap (Δ E ) of 0.63 V, featuring a high ORR half-wave potential of 0.85 V and a low OER potential of 1.48 V at 10 mA cm −2 . When integrated into an RZAB, the air cathode delivers a high peak power density of 162.8 mW cm −2 and exceptional ultralong cycling stability over 1600 h. This work establishes a generalizable method based on precise electronic-structure engineering via interfacial electron bridging for designing robust electrocatalysts.