Impact of Acid Sites in ZSM-5 Zeolites on the Selective Catalytic Oxi-Upcycling of High-Density Polyethylene to Dicarboxylic Acid under Mild Conditions

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-08-27 DOI:10.1021/acscatal.4c04987

Fan Yuan, Xueyang Hou, Kaili Wang, Yi Zhu, Guoli Chen, Yi Hao, Jingxiu Yang, Jingfeng Han, Rongrong Jia, Pimjai Pimbaotham, Yuwanda Injongkol, Siriporn Jungsuttiwong, Liyi Shi, Ping Cheng and Lei Huang*,

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Abstract

The catalytic oxidation strategy has shown great potential in the upcycling of polyethylene (PE) into valuable chemicals that contain oxygenated groups. The development of inexpensive and efficient catalysts is highly required but remains challenging. Herein, we report that ZSM-5 zeolites could be used as an effective catalyst for the selective catalytic oxi-upcycling of high-density polyethylene (HDPE) into dicarboxylic acids within the C₄–C₁₇ range at 160 °C and 1.5 MPa air pressure with a reaction duration of 16 h. Among the three tested ZSM-5 zeolites (Si/Al = 38, 70, and 170), the sample with a Si/Al ratio of 38 exhibited the highest acid site density and, consequently, the best catalytic activity. Based on the model molecular reactions, detected intermediate species, and theoretical calculation, we propose that Bro̷nsted acid sites synergize with oxygen to drive the oxidation of PE via a carbenium ion (C⁺) mediated mechanism, which is beyond the conventional pathway of direct oxidation of PE molecular chains by a free radical mechanism. Besides, the ZSM-5 zeolite has the potential to be applied broadly in the oxi-upcycling of different PE feedstocks and PE plastic wastes.

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ZSM-5分子筛中酸位对高密度聚乙烯在温和条件下选择性催化氧化升级回收制二羧酸的影响

催化氧化策略在将聚乙烯（PE）升级为含有氧基的有价值化学品方面显示出巨大的潜力。开发廉价高效的催化剂是非常必要的，但仍然具有挑战性。本文报道了ZSM-5分子筛可以作为一种有效的催化剂，在160℃、1.5 MPa的空气压力下，在C4-C17范围内选择性催化高密度聚乙烯（HDPE）氧化升级为二羧酸，反应时间为16小时。在三种测试的ZSM-5分子筛（Si/Al = 38、70和170）中，Si/Al比为38的样品具有最高的酸位密度，因此具有最佳的催化活性。基于模型分子反应、检测到的中间体种类和理论计算，我们提出了通过碳离子（C+）介导的机制与氧协同作用驱动PE氧化，而不是通过自由基机制直接氧化PE分子链。此外，ZSM-5分子筛在不同PE原料和PE塑料废弃物的氧化升级回收中具有广泛的应用潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.