Abstract Elaborating electrooxidation mechanisms of biomass molecules on transition‐metal‐based electrodes is crucial to designing high‐performance active sites. Herein, we unveiled the direct oxidation mechanism of three electrode models, Co 4 N, CoO, and Co 4 N–CoO, in which the adsorptions of OH − and glycerol on the electrodes were competitive. The adsorption of glycerol on Co 4 N was quite strong but weak on CoO, whereas the CoO preferred to adsorb OH − species. The one‐sided adsorption properties of surface reactants led to the sluggish electrooxidation kinetics of organics on Co 4 N and CoO. Constructing Co 4 N–CoO heterointerfaces significantly balanced the one‐sided adsorption features. Due to the moderate OH − and glycerol adsorptions on Co 4 N–CoO, the OH − was mainly used to activate glycerol rather than trigger the oxidative reconstruction of materials to form high‐valence OER sites. Consequently, the Co 4 N–CoO showed excellent glycerol oxidation properties. The Co 4 N–CoO delivered a lower Tafel slope of 178 mV dec −1 while achieving a high formate yield rate of 29.40 mmol cm −2 h −1 . Furthermore, the Faradaic efficiency (FE) of formate was maintained above 90% in a 120‐h electrolysis. In situ Raman and attenuated total reflection Fourier transform infrared spectroscopy (ATR‐FTIR) experiments and DFT simulations unraveled that the improved GOR performance was mainly ascribed to the balanced co‐adsorptions of OH − and organics on Co 4 N–CoO interfaces.
Long et al. (Mon,) studied this question.