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通过具有氯脱附和中间快速氧化双反应通道的合理设计的CuSO/TiO实现1,2 - 二氯乙烷的高效深度破坏

Rationally Engineered CuSO/TiO with Cl Desorption and Intermediate Rapid Oxidation Dual-Reaction Channels for Efficacious 1,2-Dichloroethane Deep Destruction.

作者信息

Tian Mingjiao, Li Jianrong, Xu Han, Yu Yanke, Yang Qin, Jiang Zeyu, Jian Yanfei, He Chi

机构信息

Department of Environmental Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, P. R. China.

State Key Laboratory of Advanced Environmental Technology, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, P. R. China.

出版信息

Environ Sci Technol. 2025 Jul 29;59(29):15493-15503. doi: 10.1021/acs.est.5c04429. Epub 2025 Jul 20.

Abstract

Suppressing toxic polychlorinated byproducts during chlorinated volatile organic compound (CVOC) destruction remains a critical challenge. Strengthening the Cl desorption and promoting rapid deep oxidation of reaction intermediates, thereby cutting off the interaction between Cl and reaction intermediates, is an effective strategy to prevent the formation of polychlorinated byproducts. Herein, a CuSO/TiO catalyst with dual-reaction channels was developed for 1,2-dichloroethane (1,2-DCE) oxidation, featuring S═O-H sites for Cl desorption and Cu-O-S sites for intermediate oxidation. It achieved 90% conversion at 251 °C, with reaction rates 8.3 and 11.0 times higher than those of SO/TiO and CuO/TiO, respectively. The hybridization of Cu 3d-O 2p enhanced electron transfer of O → Cu, accelerating 1,2-DCE oxidation via the C═C-OH → - COO/C═O → CO pathway. Meanwhile, the Cl species generated after C-Cl dissociation combined with S═O-H and desorbed in the form of HCl, avoiding Cl binding to intermediates and thus inhibiting the generation of CHCl, CHCl, CHCl, CCl, CHClCHCl, and CClCCl. Notably, the S═O-H species as a dynamic H transfer site could capture the H of the activated intermediates after being consumed by the Cl species during the reaction, restoring the S═O-H structure and achieving stable desorption of Cl species. This study highlights the previously overlooked matching of chlorine desorption with the intermediate oxidation process, offering a highly efficient solution for CVOC purification.

摘要

在氯化挥发性有机化合物(CVOC)销毁过程中抑制有毒多氯副产物仍然是一项严峻挑战。加强氯解吸并促进反应中间体的快速深度氧化,从而切断氯与反应中间体之间的相互作用,是防止多氯副产物形成的有效策略。在此,开发了一种具有双反应通道的CuSO/TiO催化剂用于1,2-二氯乙烷(1,2-DCE)氧化,其具有用于氯解吸的S═O-H位点和用于中间体氧化的Cu-O-S位点。它在251℃时实现了90%的转化率,反应速率分别比SO/TiO和CuO/TiO高8.3倍和11.0倍。Cu 3d-O 2p的杂化增强了O→Cu的电子转移,通过C═C-OH→-COO/C═O→CO途径加速了1,2-DCE氧化。同时,C-Cl解离后产生的氯物种与S═O-H结合并以HCl的形式解吸,避免了氯与中间体结合,从而抑制了CHCl、CHCl、CHCl、CCl、CHClCHCl和CClCCl的生成。值得注意的是,S═O-H物种作为动态氢转移位点,在反应过程中被氯物种消耗后可以捕获活化中间体的氢,恢复S═O-H结构并实现氯物种的稳定解吸。本研究突出了先前被忽视的氯解吸与中间体氧化过程的匹配,为CVOC净化提供了一种高效解决方案。

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