“Vacancy mediated internal-external synergy” regulation strategy on constructing defect-engineered non-noble metal catalysts for electrooxidation of glycerol

The electrooxidation of glycerol (GOR) represents a prospective environmentally friendly approach for the production of value-added biomass-derived chemicals. However, this reaction is hindered by significant barriers arising from the adsorption and coupling of glycerol molecules and active hydroxyl species (OH − ) on the catalytic surface, which severely constrains catalytic efficiency. In this study, a copper-based catalytic electrode enriched with oxygen vacancies (V O -CuO x /CF) is developed to optimize adsorption behavior via a synergistic dual mechanism: providing extra adsorption sites and fine-tuning the d-band center of the material from both extrinsic and intrinsic perspectives. Using density functional theory calculations and electrochemical testing, the introduction of oxygen vacancies (V O ) optimizes the adsorption process and enhance the adsorption capacity of both OH − and glycerol molecules. As a result, the V O -enriched catalyst exhibits reduced charge transfer resistance and remarkable deep oxidation capability. Exceptional GOR performance is achieved, including an extremely low onset potential of 1.10 V RHE and a high formate selectivity of 95.83%. Besides, continuous generation of formate and H 2 is accomplished in a two-electrode flow cell electrolyzer. This study provides essential insights into the optimization of adsorption sites and established a robust framework designing of efficient electrocatalysts for the electrooxidation of biomass-derived platform molecules.