The electrooxidation of 5-hydroxymethylfurfural (HMF) offers a promising green route to attain high-value chemicals from biomass. The HMF electrooxidation reaction (HMFOR) is a complicated process involving the combined adsorption and coupling of organic molecules and OH− on the electrode surface. An in-depth understanding of these adsorption sites and reaction processes on electrocatalysts is fundamentally important. Herein, the adsorption behavior of HMF and OH−, and the role of oxygen vacancy on Co3O4 are initially unraveled. Correspondingly, instead of the competitive adsorption of OH− and HMF on the metal sites, it is observed that the OH− can fill into oxygen vacancy (Vo) prior to couple with organic molecules through lattice oxygen oxidation reaction process, which could accelerate the rate-determining step of the dehydrogenation of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) intermediates. With the modulated adsorption sites, the as-designed Vo-Co3O4 shows excellent activity for HMFOR with the earlier potential of 90 and 120 mV at 10 mA cm−2 in 1 m KOH and 1 m PBS solution. This work sheds insight on the catalytic mechanism of oxygen vacancy, which benefits designing a novel electrocatalysts to modulate the multi-molecules combined adsorption behaviors.
