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

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, Co₄N, CoO, and Co₄N-CoO, in which the adsorptions of OH^- and glycerol on the electrodes were competitive. The adsorption of glycerol on Co₄N 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 Co₄N and CoO. Constructing Co₄N-CoO heterointerfaces significantly balanced the one-sided adsorption features. Due to the moderate OH^- and glycerol adsorptions on Co₄N-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 Co₄N-CoO showed excellent glycerol oxidation properties. The Co₄N-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 Co₄N-CoO interfaces.