Pyridinic‐N‐Cu‐Se Interfacial Synergy Enables Stable Bifunctional Oxygen Electrocatalysis

Abstract Transition metal selenides (TMSes) have garnered significant attention as bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable zinc‐air batteries (ZABs). However, their catalytic performance and durability remain constrained by the low‐activity interfacial environments. Herein, synergistic pyridinic‐N‐Cu‐Se interfacial configurations are designed and constructed on 3D nitrogen‐doped carbon nanosheets (Cu 2‐x Se@3D‐NCNs) via a molten salt‐assisted strategy. Theoretical simulations and in situ spectroscopic analyses reveal that the pyridinic‐N‐Cu‐Se interface induces a significant downshift of the Cu d ‐band center, optimizes adsorption of oxygen species, and drives dynamic surface reconstruction into amorphous oxyhydroxide species under OER conditions. These oxyhydroxides serve as the true active phase for OER, while coordination‐driven electronic modulation of Cu sites facilitates adsorption of oxygen intermediates during ORR, thereby enhancing reaction kinetics. As a result, Cu 2‐x Se@3D‐NCNs exhibits excellent bifunctional activity, featuring a low potential gap (Δ E = 0.76 V), a high peak power density (103.8 mW cm −2 ), and extended cycling life (750 cycles) in aqueous ZABs. Furthermore, the assembled flexible ZABs demonstrate stable performance under mechanical deformation, highlighting its potential for next‐generation wearable energy storage systems. This work underscores the critical role of interfacial coordination engineering in the development of durable and efficient bifunctional electrocatalysts.