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Abstract

The majority of energy conversion processes such as hydrogen peroxide production, nitrogen fixation, and CO₂ reduction generally involve multi-electron transfer, resulting in multiple by-products and requiring tedious purification process. The development of highly selective electrocatalysts can not only reduce the energy consumption in the production process but also benefit to promote their large-scale application. Here, we report an asymmetric ligand design of molecular “Venus flytrap” at atomic Co^II catalysts on a heterogeneous carbon surface for oxygen electrocatalysis with controlled selectivity. Our XAFS and DFT calculations show that the strong-field ligand-induced LS Co^II centers offer inimitable steric-electronic advantages in capturing O₂ and the capability to regulate reaction pathways through an H-bonding interaction between the ligands and peroxo intermediate. The proposed concept completes the picture of designer single-atom catalyst by covering the often overlooked exterior coordination sites, and is expected to be generally applicable to other heterogeneous catalyst systems.