Electro‐Oxidation of Glycerol to Formate at Near‐Zero Potential Driven by Cathodic Oxygen Reduction‐Generated *OH

ABSTRACT Electrochemical oxidation of glycerol to formate via C─C bond cleavage has emerged as an attractive technology for the conversion of surplus glycerol into diverse high‐value chemicals; yet the performance is limited by the high anodic potential as the reaction typically follows the oxygen evolution reaction (OER)‐coupled pathway. In this study, we demonstrate that glycerol oxidation to formate can be mediated by the cathodic oxygen reduction reaction (ORR) instead at near‐zero potential. Among the model catalysts with different ORR selectivity, oxygen‐doped carbon (O‐C NP ) stands out as the best catalyst for glycerol oxidation with 91.0% formate selectivity, producing 246 mM formate at −0.3 V versus RHE after 8 h. Such a performance is comparable to that with state‐of‐the art OER‐coupled strategy operated at potentials over +1.3 V versus RHE. The selective glycerol oxidation at low cathodic potentials is driven by the active *OH species generated during ORR, as evidenced by in situ spectroscopy and radical quantification and quenching experiments. Computational studies reveal that the generation of *OH and the mediation in glycerol oxidation are thermodynamically favorable on O‐C NP as compared to others in the series. This work paves a new avenue for glycerol oxidation via cathodic reactive oxygen species mediation.