Sulfur-bridge ligands altering the microenvironment of single-atom CoNS sites to boost the oxygen reduction reaction

We report here an asymmetric N,S-coordinated cobalt-based single-atom catalyst with sulfur (S)-bridge ligands (Co-N/S-C) for the oxygen reduction reaction (ORR). The Co-N/S-C exhibits a half-wave potential ( E 1/2 ) of 0.908 V versus RHE, outperforming most state-of-the-art ORR catalysts. Theoretical calculations indicate that the CoN 3 SC 10 -S moiety facilitates the ORR kinetics by optimizing the adsorption of intermediates. This work provides new insights into the design of single-atom catalysts for electrocatalysis through heteroatom-bridge ligand engineering. The unique S-bridge ligands' synergistic CoN 3 S sites in Co-N/S-C have optimal adsorption-desorption and lower energy barriers of ORR intermediates, thus boosting the ORR activity.