Li Cheng-Peng, Li Hai-Ruo, Ai Jin-Yun, Chen Jing, Du Miao
College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387, China.
College of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China.
ACS Cent Sci. 2020 Dec 23;6(12):2354-2361. doi: 10.1021/acscentsci.0c01342. Epub 2020 Nov 30.
Metal-organic frameworks (MOFs) are a class of promising sorbents for effective sequestration of radioactive TcO anions. However, their poor stability and slow sorption kinetics in the industrial condition pose a great challenge. Herein, we demonstrate an optimizing strategy via polymerization of ionic liquids (ILs) encapsulated in the pores of MOFs, forming polyILs@MOFs composites with greatly enhanced TcO sequestration compared with the pristine MOFs. Notably, the cross-linked polymerization of ILs facilitates the formation of both the inside ionic filler as the active sites and outside coating as the protective layers of MOFs, which is significantly beneficial to obtain the optimized sorption materials of exceptional stability under extreme conditions (e.g., in 6 M HNO). The final optimized composite shows fast sorption kinetics (<30 s), good regeneration (>30 cycles), and superior uptake performance for TcO in highly acidic conditions and simulated recycle stream. This strategy opens up a new opportunity to construct the highly stable MOF-based composites and extend their applicability in different fields.
金属有机框架材料(MOFs)是一类很有前景的吸附剂,可有效螯合放射性TcO 阴离子。然而,它们在工业条件下稳定性差且吸附动力学缓慢,这带来了巨大挑战。在此,我们展示了一种优化策略,即通过聚合封装在MOF孔中的离子液体(ILs),形成聚离子液体@MOF复合材料,与原始MOF相比,其对TcO 的螯合能力大大增强。值得注意的是,离子液体的交联聚合促进了作为活性位点的内部离子填料和作为MOF保护层的外部涂层的形成,这对于在极端条件下(例如在6 M HNO中)获得具有出色稳定性的优化吸附材料非常有益。最终优化后的复合材料显示出快速的吸附动力学(<30秒)、良好的再生性能(>30次循环),并且在高酸性条件和模拟循环流中对TcO 具有优异的吸附性能。该策略为构建高度稳定的基于MOF的复合材料并扩展其在不同领域的适用性开辟了新机会。