Selective Upcycling of Polyethylene Terephthalate towards High‐valued Oxygenated Chemical Methyl p‐Methyl Benzoate using a Cu/ZrO2 Catalyst

Abstract Upgrading of polyethylene terephthalate (PET) waste into valuable oxygenated molecules is a fascinating process, yet it remains challenging. Herein, we developed a two‐step strategy involving methanolysis of PET to dimethyl terephthalate (DMT), followed by hydrogenation of DMT to produce the high‐valued chemical methyl p‐methyl benzoate (MMB) using a fixed‐bed reactor and a Cu/ZrO 2 catalyst. Interestingly, we discovered the phase structure of ZrO 2 significantly regulates the selectivity of products. Cu supported on monoclinic ZrO 2 (5 %Cu/m‐ZrO 2 ) exhibits an exceptional selectivity of 86 % for conversion of DMT to MMB, while Cu supported on tetragonal ZrO 2 (5 %Cu/t‐ZrO 2 ) predominantly produces p‐xylene (PX) with selectivity of 75 %. The superior selectivity of MMB over Cu/m‐ZrO 2 can be attributed to the weaker acid sites present on m‐ZrO 2 compared to t‐ZrO 2 . This weak acidity of m‐ZrO 2 leads to a moderate adsorption capability of MMB, and facilitating its desorption. Furthermore, DFT calculations reveal Cu/m‐ZrO 2 catalyst shows a higher effective energy barrier for cleavage of second C−O bond compared to Cu/t‐ZrO 2 catalyst; this distinction ensures the high selectivity of MMB. This catalyst not only presents an approach for upgrading of PET waste into fine chemicals but also offers a strategy for controlling the primary product in a multistep hydrogenation reaction.