Unraveling the Impact of Oxygen Vacancy on Electrochemical Valorization of Polyester Over Spinel Oxides

Electrochemical upcycling of end‐of‐life polyethylene terephthalate (PET) using renewable electricity offers a route to generate valuable chemicals while processing plastic wastes. However, it remains a huge challenge to design an electrocatalyst with reliable structure‐property relationships for PET valorization. Herein, spinel Co3O4 with rich oxygen vacancies for improved activity toward formic acid (FA) production from PET hydrolysate is reported. Experimental investigations combined with theoretical calculations reveal that incorporation of VO into Co3O4 not only promotes the generation of reactive hydroxyl species (OH*) species at adjacent tetrahedral Co2+ (Co2+ Td), but also induces an electronic structure transition from octahedral Co3+ (Co3+ Oh) to octahedral Co2+ (Co2+ Oh), which typically functions as highly‐active catalytic sites for ethylene glycol (EG) chemisorption. Moreover, the enlarged Co‐O covalency induced by VO facilitates the electron transfer from EG* to OH* via Co2+ Oh‐O‐Co2+ Td interaction and the following C─C bond cleavage via direct oxidation with a glyoxal intermediate pathway. As a result, the VO‐Co3O4 catalyst exhibits a high half‐cell activity for EG oxidation, with a Faradaic efficiency (91%) and productivity (1.02 mmol cm−2 h−1) of FA. Lastly, it is demonstrated that hundred gram‐scale formate crystals can be produced from the real‐world PET bottles via two‐electrode electroreforming, with a yield of 82%. Incorporation of oxygen vacancy into Co3O4 not only realizes an electronic structure transition from poorly‐active octahedral Co3+ to highly‐active octahedral Co2+, thereby facilitating ethylene glycol (EG) adsorption on Co3O4, but also allows for a promoted reactive hydroxyl species generation at the adjacent tetrahedral Co2+ sites, which accelerates EG oxidation for formic acid production via direct oxidation mechanism.