Coordinating the Competitive Adsorption of Organic and OH − to Accelerate Electrooxidation Kinetics of Biomass‐Derived Nucleophiles

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.