Oxidation of renewable polyol/sugar into formic acid using molecular O₂over heterogeneous catalysts is still challenging due to the insufficient activation of both O₂and organic substrates on coordination-saturated metal oxides. In this study, we develop a defective MnO₂catalyst through a coordination number reduction strategy to enhance the aerobic oxidation of various polyols/sugars to formic acid. Compared to common MnO₂, the tri-coordinated Mn in the defective MnO₂catalyst displays the electronic reconstruction of surface oxygen charge state and rich surface oxygen vacancies. These oxygen vacancies create more Mn^δ+Lewis acid site together with nearby oxygen as Lewis base sites. This combined structure behaves much like Frustrated Lewis pairs, serving to facilitate the activation of O₂, as well as C–C and C–H bonds. As a result, the defective MnO₂catalyst shows high catalytic activity (turnover frequency: 113.5 h⁻¹) and formic acid yield (>80%) comparable to noble metal catalysts for glycerol oxidation. The catalytic system is further extended to the oxidation of other polyols/sugars to formic acid with excellent catalytic performance.

Catalytic upcycling of polyethylene terephthalate (PET) into high-value oxygenated products is a fascinating process, yet it remains challenging. Here, we present a one-step tandem strategy to realize the thermal catalytic oxidation upcycling of PET to terephthalic acid (TPA) and high-value glycolic acid (GA) instead of ethylene glycol (EG). By using the Au/NiO with rich oxygen vacancies as catalyst, we successfully accelerate the hydrolysis of PET, accompanied by obtaining 99% TPA yield and 87.6% GA yield. The results reveal that the oxygen vacancies in NiO (NiO-O_v) support tend to adsorb hydrolysis product TPA, preferentially ensuring the strong adsorption of EG at the Au-NiO interface. Moreover, during the EG oxidation process, the Au-NiO interface, composed of two types of structures, quasi “AuNi alloy” and NiO-O_v, simultaneously promote the C-H bond activation, where Ni in “AuNi alloy” exhibits an oxytropism effect to anchor the C = O bond of the intermediate, while the residual O in NiO-O_v pillages the H in the C-H bond. Such Au/NiO catalyst is further extended to promote the thermal catalytic oxidation upcycling of other polyethylene glycol esters to GA with excellent catalytic performance.