Zhang Mengting, Huo Zhaojing, Li Longqian, Ji Yi, Ding Tengda, Hou Guangjin, Song Song, Dai Weili
School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, 300350, P.R. China.
State Key Laboratory of Catalysis, National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023, P. R. China.
ChemSusChem. 2025 Mar 15;18(6):e202402013. doi: 10.1002/cssc.202402013. Epub 2024 Nov 14.
Chemical upcycling of plastic wastes into valuable chemicals is a promising strategy for resolving plastic pollution, but economically viable methods currently are still lacking. Here, we report one-pot hydrogenolysis of PET plastic into p-xylene with an excellent yield (99.8 %) over a robust non-precious Cu-based catalyst, CuZn/AlO, in the absence of alcohol solvents. The presence of Zn species promotes the dispersion of Cu and increases the ratio of Cu/Cu, whereas the synergistic effect of Cu and Cu leads to a superior performance in the conversion of PET. The combination of GC-MS, C CP MAS NMR, 2D H-C CP HETCOR NMR spectroscopy and kinetic studies for the first time demonstrates 4-methyl benzyl alcohol as an important reaction intermediate in the hydrogenolysis of PET. Mechanistic studies indicate that the conversion of PET mainly follows a hydrogenolysis process, involving the cleavage of ester bonds to alcohols and the C-O bond cleavage of alcohols to alkanes. This work not only brings new insight for understanding the upgrading pathway of PET, but also provides a guidance for the design of high-performance non-precious catalysts for the chemical upcycling of plastic wastes.
将塑料废物化学升级循环为有价值的化学品是解决塑料污染的一种有前景的策略,但目前仍缺乏经济可行的方法。在此,我们报道了在无醇溶剂存在下,通过一种稳健的非贵金属铜基催化剂CuZn/AlO,将聚对苯二甲酸乙二酯(PET)塑料一锅法氢解为对二甲苯,产率优异(99.8%)。锌物种的存在促进了铜的分散并提高了Cu⁺/Cu⁰的比例,而Cu⁺和Cu⁰的协同作用导致PET转化具有卓越性能。气相色谱 - 质谱联用(GC-MS)、¹³C交叉极化魔角旋转核磁共振(¹³C CP MAS NMR)、二维¹H - ¹³C 异核多量子相干核磁共振光谱(2D ¹H - ¹³C CP HETCOR NMR)以及动力学研究首次证明4 - 甲基苄醇是PET氢解过程中的重要反应中间体。机理研究表明,PET的转化主要遵循氢解过程,包括酯键断裂生成醇以及醇的C - O键断裂生成烷烃。这项工作不仅为理解PET的升级途径带来了新的见解,也为设计用于塑料废物化学升级循环的高性能非贵金属催化剂提供了指导。