通过位点解耦铜催化解锁高浓度PET升级回收

IF 16.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI:10.1002/anie.202516357

Chuan Gang, Jingqing Tian, Bing Ma, Chen Zhao

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引用次数: 0

摘要

将岛屿上的聚对苯二甲酸乙二醇酯（PET）塑料垃圾升级为有价值的燃料是碳资源利用和循环经济发展的一个有前景的战略；然而，这种方法面临着严峻的挑战，包括低处理浓度（目前为CPET <； 1.5 wt%）和高温氧化还原条件下催化剂的快速失活。在此，我们报告了一种位点解耦铜催化剂（Cu/MgAlGaZnOx），该催化剂以前所未有的浓度（15.1 wt%）将PET定量转化为对二甲苯（PX），实现了创纪录的PX形成率，比之前的CuNa/SiO2体系高10.1 - 7.8倍。原位光谱分析表明，在解聚过程中乙二醇（EG）片段氧化减少了常规催化剂中的Cu+物种，引发了快速失活。相比之下，GaZnOx中的氧空位（Ov）支持甲醇分解中间体的吸附，在空间上分离解聚（GaZnOx）和加氢脱氧（Cu/MgAlOx）。这种去耦稳定了活性Cu + /Cu0─Ov位点，使其能够在高浓度PET下持续运行。我们的工作建立了在苛刻环境下稳定聚合物升级回收中的氧化还原催化剂的一般策略。

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Unlocking High‐Concentration PET Upcycling via Site‐Decoupled Copper Catalysis

Upcycling polyethylene terephthalate (PET) plastic waste on islands into valuable fuels represents a promising strategy for carbon resource utilization and circular economy development; however, this approach faces critical challenges, including low processing concentrations (currently CPET < 1.5 wt%) and fast catalyst deactivation under high‐temperature redox conditions. Herein, we report a site‐decoupled copper catalyst (Cu/MgAlGaZnOx) that unlocks quantitative conversion of PET to p‐xylene (PX) at unprecedented concentrations (15.1 wt%), achieving a record PX formation rate of 10.1 −7.8‐fold higher than prior CuNa/SiO2 systems. In situ spectroscopy reveals that ethylene glycol (EG) fragment oxidation during depolymerization reduces Cu+ species in conventional catalysts, triggering rapid deactivation. By contrast, oxygen vacancies (Ov) in the GaZnOx support adsorb methanolysis intermediates, spatially segregating depolymerization (GaZnOx) from hydrodeoxygenation (Cu/MgAlOx). This decoupling stabilizes active Cu⁺/Cu0─Ov sites, enabling sustained operation at high PET concentrations. Our work establishes site decoupling as a general strategy for stabilizing redox catalysts in polymer upcycling under demanding environments.

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来源期刊

Angewandte Chemie International Edition 化学-化学综合

CiteScore

26.60

自引率

6.60%

发文量

3549

审稿时长

1.5 months

期刊介绍： Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.