Electrosynthesis of Hydrogen Peroxide Synergistically Catalyzed by Atomic Co–N x –C Sites and Oxygen Functional Groups in Noble‐Metal‐Free Electrocatalysts

Abstract Hydrogen peroxide (H 2 O 2 ) is a green oxidizer widely involved in a vast number of chemical reactions. Electrochemical reduction of oxygen to H 2 O 2 constitutes an environmentally friendly synthetic route. However, the oxygen reduction reaction (ORR) is kinetically sluggish and undesired water serves as the main product on most electrocatalysts. Therefore, electrocatalysts with high reactivity and selectivity are highly required for H 2 O 2 electrosynthesis. In this work, a synergistic strategy is proposed for the preparation of H 2 O 2 electrocatalysts with high ORR reactivity and high H 2 O 2 selectivity. A Co−N x −C site and oxygen functional group comodified carbon‐based electrocatalyst (named as Co–POC–O) is synthesized. The Co–POC–O electrocatalyst exhibits excellent catalytic performance for H 2 O 2 electrosynthesis in O 2 ‐saturated 0.10 m KOH with a high selectivity over 80% as well as very high reactivity with an ORR potential at 1 mA cm −2 of 0.79 V versus the reversible hydrogen electrode (RHE). Further mechanism study identifies that the Co−N x −C sites and oxygen functional groups contribute to the reactivity and selectivity for H 2 O 2 electrogeneration, respectively. This work affords not only an emerging strategy to design H 2 O 2 electrosynthesis catalysts with remarkable performance, but also the principles of rational combination of multiple active sites for green and sustainable synthesis of chemicals through electrochemical processes.