Symmetry Breaking in Rationally Designed Copper Oxide Electrocatalyst Boosts the Oxygen Reduction Reaction

Abstract Oxygen reduction reaction (ORR) kinetics is critically dependent on the precise modulation of the interactions between the key oxygen intermediates and catalytic active sites. Herein, a novel electrocatalyst is reported, featuring nitrogen‐doped carbon‐supported ultra‐small copper oxide nanoparticles with the broken‐symmetry C _4v coordination filed sites, achieved by a mild γ‐ray radiation‐induced method. The as‐synthesized catalyst exhibits an excellent ORR activity with a half‐wave potential of 0.873 V and shows no obvious decay over 50 h durability in alkaline solution. This superior catalytic activity is further corroborated by the high‐performance in both primary and rechargeable Zn–air batteries with an ultrahigh‐peak‐power density (255.4 mW cm ⁻² ) and robust cycling stability. The experimental characterizations and density functional theory calculations show that the surface Cu atoms are configured in a compressed octahedron coordination. This geometric arrangement interacts with the key intermediate OH ^* , facilitating localized charge transfer and thereby weakening the Cu─O bond, which promotes the efficient transformation of OH ^* to OH ⁻ and the subsequent desorption, and markedly accelerates kinetics of the rate‐determining step in the reaction. This study provides new insights for developing the utilization of γ‐ray radiation chemistry to construct high‐performance metal oxide‐based catalysts with broken symmetry toward ORR.