Sulfur filling activates vacancy-induced C-C bond cleavage in polyol electrooxidation.

Using the electrochemical polyol oxidation reaction (POR) to produce formic acid over nickel-based oxides/hydroxides (NiO x H y ) is an attractive strategy for the electrochemical upgrading of biomass-derived polyols. The key step in the POR, i.e. the cleavage of the C-C bond, depends on an oxygen-vacancy-induced mechanism. However, a high-energy oxygen vacancy is usually ineffective for Schottky-type oxygen-vacancy-rich β-Ni(OH) 2 (V SO -β-Ni(OH) 2 ). As a result, both β-Ni(OH) 2 and V SO -β-Ni(OH) 2 cannot continuously catalyze oxygen-vacancy-induced C-C bond cleavage during PORs. Here, we report a strategy of oxygen-vacancy-filling with sulfur to synthesize a β-Ni(OH) 2 (S-V O -β-Ni(OH) 2 ) catalyst, whose oxygen vacancies are protected by filling with sulfur atoms. During PORs over S-V O -β-Ni(OH) 2 , the pre-electrooxidation-induced loss of sulfur and structural self-reconstruction cause the in-situ generation of stable Frenkel-type oxygen vacancies for activating vacancy-induced C-C bond cleavage, thus leading to excellent POR performances. This work provides an intelligent approach for guaranteeing the sustaining action of the oxygen-vacancy-induced catalytic mechanism in electrooxidation reactions.