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Cooperative Catalysis toward Oxygen Reduction Reaction under Dual Coordination Environments on Intrinsic AMnO 3 ‐Type Perovskites via Regulating Stacking Configurations of Coordination Units
Author(s) -
Zhao Chunning,
Zhang Xilin,
Yu Meng,
Wang Ansheng,
Wang Linxia,
Xue Lina,
Liu Jieyu,
Yang Zongxian,
Wang Weichao
Publication year - 2020
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.202006145
Subject(s) - stacking , catalysis , materials science , overpotential , octahedron , redox , chemical physics , crystallography , electrochemistry , chemistry , crystal structure , organic chemistry , electrode , metallurgy
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.