Zou Qizhuang, Long Tairen, Fang Ruiqi, Zhao Xin, Wang Fengliang, Li Yingwei
Guangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 360015, China.
Angew Chem Int Ed Engl. 2025 Jul 21;64(30):e202507309. doi: 10.1002/anie.202507309. Epub 2025 May 24.
Exploring an efficient catalytic system for tandem upcycling of CO and polyethylene terephthalate (PET) is highly desirable for achieving efficient resource utilization of wastes. However, the high activation energy for C═O bonds (in both PET and CO) and the difficulty in regulating the reaction pathways restricted PET recovery efficiency. Here, we demonstrated the rational design of a single-atom Cu catalyst for precisely catalyzing the hydrogenation of CO to methanol and tandem PET upcycling to ethylene glycol (EG) and p-xylene (PX). In the Cu/UiO-66-NH-A catalyst, Cu atoms are selectively anchored to the Zr-oxo nodes of UiO-66-NH to form Cu-O-Zr sites. The Cu-O-Zr sites can effectively activate both CO and H by reducing the activation energy and accelerate the transformation of PET to dimethyl terephthalate (DMT), which is further hydro-deoxygenated to yield PX. As a result, 20.4% CO conversion was obtained within 36 h, with 89.5% and 92.1% yields of PX and EG, respectively. Rapid and precise hydrogen spillover from Cu atoms to adsorbed reactants/intermediates at the Cu-O-Zr sites also drives the reaction process.
探索一种用于一氧化碳（CO）和聚对苯二甲酸乙二酯（PET）串联升级回收的高效催化体系，对于实现废物的高效资源利用非常必要。然而，C═O键（在PET和CO中）的高活化能以及反应路径调控的困难限制了PET的回收效率。在此，我们展示了一种单原子铜催化剂的合理设计，用于精确催化CO加氢制甲醇以及PET串联升级回收为乙二醇（EG）和对二甲苯（PX）。在Cu/UiO-66-NH-A催化剂中，铜原子选择性地锚定在UiO-66-NH的Zr-氧节点上形成Cu-O-Zr位点。Cu-O-Zr位点可以通过降低活化能有效地活化CO和H，并加速PET向对苯二甲酸二甲酯（DMT）的转化，DMT进一步加氢脱氧生成PX。结果，在36小时内实现了20.4%的CO转化率，PX和EG的产率分别为89.5%和92.1%。Cu原子在Cu-O-Zr位点上向吸附的反应物/中间体的快速且精确的氢溢流也推动了反应过程。
