Boosting Oxygen Reduction for High‐Efficiency H 2 O 2 Electrosynthesis on Oxygen‐Coordinated CoNC Catalysts

Abstract Atomically dispersed CoNC is a promising material for H 2 O 2 selective electrosynthesis via a two‐electron oxygen reduction reaction. However, the performance of typical CoNC materials with routine CoN 4 active center is insufficient and needs to be improved further. This can be done by fine‐tuning its atomic coordination configuration. Here, a single‐atom electrocatalyst (Co/NC) is reported that comprises a specifically penta‐coordinated CoNC configuration (OCoN 2 C 2 ) with Co center coordinated by two nitrogen atoms, two carbon atoms, and one oxygen atom. Using a combination of theoretical predictions and experiments, it is confirmed that the unique atomic structure slightly increases the charge state of the cobalt center. This optimizes the adsorption energy towards *OOH intermediate, and therefore favors the two‐electron ORR relevant for H 2 O 2 electrosynthesis. In neutral solution, the as‐synthesized Co/NC exhibits a selectivity of over 90% over a potential ranging from 0.36 to 0.8 V, with a turnover frequency value of 11.48 s −1 ; thus outperforming the state‐of‐the‐art carbon‐based catalysts.