Olefin-linked cationic covalent organic frameworks for efficient extraction of ReO4-/99TcO4.
Olefin-linked cationic covalent organic frameworks for efficient extraction of ReO4-/99TcO4.
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DOI：
10.1016/j.jhazmat.2022.130603
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发表时间：
2022-12
影响因子：
13.6
通讯作者：
Wei-Rong Cui;Wei Xu;Yi-Ru Chen;Kai Liu;Wei-Bin Qiu;Yibao Li;Jianding Qiu
中科院分区：
文献类型：
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作者：
Wei-Rong Cui;Wei Xu;Yi-Ru Chen;Kai Liu;Wei-Bin Qiu;Yibao Li;Jianding Qiu
利用多孔吸附剂从强酸/强碱溶液中有效提取放射性~（99）TcO ~（4-）是一个非常理想的方法，但仍然是一个很大的挑战。为了克服这一挑战，在这里，我们报告了具有优异的酸、碱和辐射稳定性的烯烃连接的阳离子共价有机框架（COF）的第一个实例，其命名为BDBI-TMT，其通过将稳健的基于咪唑盐的连接体与三嗪结构单元整合而合成。BDBI-TMT显示出超快的吸附动力学（在1分钟内达到平衡）和726 mg g−1的优异ReO 4-（99 TcO 4-的非放射性替代物）捕获能力，这可以归因于在有序孔道的高度可及的孔壁上精确定制的咪唑鎓盐基单元的丰度。此外，高共轭大体积烷基骨架的形成增强了BDBI-TMT的疏水性，这不仅显着提高了对ReO 4-/99 TcO 4-的亲和力，而且还提高了化学稳定性，即使在极端条件下也可以选择性和可逆地萃取ReO 4-/99 TcO 4-。本工作表明了烯烃连接的阳离子COFs对ReO 4-/99 TcO 4-萃取的巨大潜力，为构建高性能的放射性核素修复多孔吸附剂提供了新的途径。
Efficient extraction of radioactive99TcO4-from strong acid/base solutions by porous adsorbents is extremely desirable but remains a great challenge. To overcome the challenge, here we report the first example of an olefin-linked cationic covalent organic framework (COF) named BDBI-TMT with excellent acid, base and radiation stability is synthesized by integrating robust imidazolium salt-based linkers with triazine building blocks. BDBI-TMT shows an ultra-fast adsorption kinetics (equilibrium is reached within 1 min) and an excellent ReO4-(a non-radioactive surrogate of99TcO4-) capture capacity of 726 mg g−1, which can be attributed to the abundance of precisely tailored imidazolium salt-based units on the highly accessible pore walls of the ordered pore channels. Furthermore, the formation of the highly conjugated bulky alkyl skeleton enhances the hydrophobicity of BDBI-TMT, which significantly improves not only the affinity toward ReO4-/99TcO4-but also the chemical stability, allowing selective and reversible extraction of ReO4-/99TcO4-even under extreme conditions. This work demonstrates the great potential of olefin-linked cationic COFs for ReO4-/99TcO4-extraction, providing a new avenue to construct high-performance porous adsorbents for radionuclide remediation.