Cooperative Catalysis toward Oxygen Reduction Reaction under Dual Coordination Environments on Intrinsic AMnO3‐Type Perovskites via Regulating Stacking Configurations of Coordination Units

Abstract It remains challenging for pure‐phase catalysts to achieve high performance during the electrochemical oxygen reduction reaction to overcome the sluggish kinetics without the assistance of extrinsic conditions. Herein, a series of pristine perovskites, i.e., AMnO 3 (A = Ca, Sr, and Ba), are proposed with various octahedron stacking configurations to demonstrate the cooperative catalysis over SrMnO 3 jointly explored by experiments and first‐principles calculations. Comparing with the unitary stacking of coordination units in CaMnO 3 or BaMnO 3 , the intrinsic SrMnO 3 with a mixture of corner‐sharing and face‐sharing octahedron stacking configurations demonstrates superior activity ( E half‐wave = 0.81 V), and charge–discharge stability over 400 h without the voltage gap (≈0.8 V) increasing in zinc–air batteries. The theoretical study reveals that, on the SrMnO 3 (110) surface, the active sites switch from coordinatively unsaturated atop Mn (*OO, *OOH) to Mn–Mn bridge (*O, *OH). Therefore, the intrinsic dual coordination environments of Mn–O corner and Mn–O face enable cooperative modulation of the interaction strength of the oxygen intermediates with the surface, inducing the decrease of the *OH desorption energy (rate‐limiting step) unrestricted by scaling relationships with the overpotential of ≈0.28 V. This finding provides insights into catalyst design through screening intrinsic structures with multiple coordination unit stacking configurations.