Local Geometric Distortion to Stimulate Oxygen Reduction Activity of Atomically Dispersed Zn‐Nx Sites for Zn–Air Batteries

Abstract Local geometric strain engineering is useful for modulating the performance of nitrogen‐coordinated transition metal‐carbon catalysts. However, realizing the nano‐level strain is technically challenging. Additionally, the structure‐property relationship between strain degree and performance remains poorly understood. Herein, it is conceptually predict that geometric bending induces more electron transfer from Zn to the coordinated N in Zn─N─C, leading to a positive shift of the d‐band center of the Zn atom, which promotes the adsorption reduction process of the O 2 molecule and thus increases the intrinsic oxygen reduction reaction (ORR) activity. Moreover, a low‐temperature non‐saturated coordination strategy is proposed to prepare spherical porous carbon catalysts with surface‐enriched geometrically bent (20‐50°) Zn─N─C sites. Benefiting from the highly active Zn─N─C sites, large specific surface area and abundant pore structure, the optimized catalyst (S─Zn─N─C‐950) exhibited excellent intrinsic alkaline ORR activity (half‐wave potential E 1/2 = 0.89 V) and high zinc‐air battery performance (peak power density of 229.2 mW cm −2 ), exceeding that of commercial Pt/C catalysts. Density functional theory (DFT) calculations show that when the geometrical bending angle is 30–45°, Zn centers with suitable charge transfer to the surrounding N can produce a moderate adsorption strength to the oxygen intermediate state, resulting in optimal ORR activity.