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

Abstract 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 Co 3 O 4 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 V O into Co 3 O 4 not only promotes the generation of reactive hydroxyl species (OH * ) species at adjacent tetrahedral Co 2+ (Co2+ Td), but also induces an electronic structure transition from octahedral Co 3+ (Co3+ Oh) to octahedral Co 2+ (Co2+ Oh), which typically functions as highly‐active catalytic sites for ethylene glycol (EG) chemisorption. Moreover, the enlarged Co‐O covalency induced by V O 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 V O ‐Co 3 O 4 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%.