The connection configuration of active sites plays a crucial role in electrocatalytic O2 evolution. Reasonably integrating the advantages of different connection configurations can enhance the catalytic performance. Here, we report a Ba0.5Sr0.5Co0.8Fe0.2O3-δ electrocatalyst featuring edge-sharing [Co/FeO6] motifs surface, constructed through an innovative Cu+-assisted top-down topological rearrangement. Our study demonstrates that the edge-sharing [Co/FeO6] motifs exhibit high lattice oxygen redox activity as well as the abilities to stabilize high-oxidation-state Co3+/4+ species and accelerate hydroxyl aggregation, thereby facilitating intermolecular O-O coupling mechanism during O2 evolution. The inner corner-sharing [Co/FeO6] motifs function as a current collector to enhance conductivity. As-synthesized electrocatalyst with these excellet properties achieves a low overpotential of 298 mV and stable operation for 100 h at 10 mA cm−2 in 1 M KOH. This work clarifies the superiority of edge-sharing [Co/FeO6] motifs in oxygen evolution reaction and prove the precise manipulation of connection configuration as an effective approach for enhancing the catalytic performance.
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