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用于高效捕获TcO⁻/ReO⁻的坚固共价有机框架的后修饰

Post-Modification of a Robust Covalent Organic Framework for Efficient Sequestration of TcO /ReO.

作者信息

Zhu Lei, Li Hai-Ruo, Liu Zhao-Fei, Di Zhengyi, Xu Wengui, Zhang Libo, Li Cheng-Peng

机构信息

Department of Molecular Imaging and Nuclear Medicine, Tianjin Medical University Cancer Institute and Hospital, National Clinical Research Centre for Cancer, Tianjin's Clinical Research Centre for Cancer, Key Laboratory of Cancer Prevention and Therapy, Tianjin, 300060, China.

College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin, 300387, China.

出版信息

Chemistry. 2023 Oct 26;29(60):e202302168. doi: 10.1002/chem.202302168. Epub 2023 Sep 18.

Abstract

Nuclear industry spent fuel reprocessing and some radioactive contamination sites often involve high acidity and salinity environments. Currently developed and reported sorbents in TcO sequestration from the nuclear waste are unstable and show low adsorption efficiency in harsh conditions. To address this issue, we developed a post-synthetic modification strategy by grafting imidazole-based ionic liquids (ILs) onto the backbone of covalent organic framework (COF) via vinyl polymerization. The resultant COF-polyILs sorbent exhibits fast adsorption kinetics (<5 min) and good sorption capacity (388 mg g ) for ReO (a nonradioactive surrogate of TcO ). Outstandingly, COF-polyILs composite shows superior ReO removal even under highly acidic conditions and in the presence of excess competing ions of Hanford low-level radioactive waste stream, benefiting from the stable covalent bonds between the COF and polyILs, mass of imidazole rings, and hydrophobic pores in COF.

摘要

核工业乏燃料后处理以及一些放射性污染场地常常涉及高酸度和高盐度环境。目前已开发并报道的用于从核废料中螯合锝酸根的吸附剂不稳定,且在苛刻条件下吸附效率较低。为解决这一问题,我们通过乙烯基聚合将咪唑基离子液体(ILs)接枝到共价有机骨架(COF)主链上,开发了一种后合成改性策略。所得的COF - polyILs吸附剂对高铼酸根(锝酸根的非放射性替代物)表现出快速的吸附动力学(<5分钟)和良好的吸附容量(388 mg g)。值得注意的是,得益于COF与polyILs之间稳定的共价键、咪唑环质量以及COF中的疏水孔,COF - polyILs复合材料即使在高酸性条件下以及存在汉福德低放废物流中过量竞争离子的情况下,仍表现出优异的高铼酸根去除能力。

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