It is of great challenge to develop the effective and stable sorbents for ⁹⁹TcO₄^– sequestration from alkaline nuclear waste. In this work, we demonstrate a general strategy for the design of poly(ionic liquids)@COF composites, via in situ polymerization of imidazolium-based ionic liquids (ILs) encapsulated in the pores of covalent–organic frameworks (COFs). With regard to the polyILs@COF composites, the cross-linking polyILs endow the alkali-stable COF framework with numerous ionic fillers as the anion-exchange sites. Compared with the pristine COF, the optimized composite not only enhances the alkali resistance but also shows the excellent ReO₄^– (a surrogate of ⁹⁹TcO₄^–) removal performances of fast exchange kinetics, high uptake capacity, superior selectivity, and good reusability, even in simulated high-level waste stream at the U.S. Savannah River Site (a typical alkaline nuclear waste). The alkaline stability and selectivity of the optimized composite can be further verified by the density functional theory (DFT) calculations, indicating its unique chemical recognition of TcO₄^– over other anions with higher charge density.

中文翻译：

---

聚（离子液体）@COF Nanotrap 的配方用于从碱性核废料中高效封存高铼酸盐

开发有效且稳定的吸附剂用于⁹⁹ TcO ₄ ^-从碱性核废料中封存是一项巨大的挑战。在这项工作中，我们展示了一种设计聚（离子液体）@COF 复合材料的一般策略，即通过封装在共价有机框架（COFs）孔隙中的咪唑基离子液体（ILs）的原位聚合。对于 polyILs@COF 复合材料，交联 polyILs 赋予碱稳定的 COF 骨架以大量离子填料作为阴离子交换位点。与原始COF相比，优化后的复合材料不仅增强了耐碱性，而且表现出优异的ReO ₄ ^-（替代⁹⁹ TcO ₄^– ) 快速交换动力学、高吸收能力、卓越的选择性和良好的可重复使用性的去除性能，即使在美国萨凡纳河站点的模拟高放废物流（典型的碱性核废物）中也是如此。优化后的复合材料的碱性稳定性和选择性可以通过密度泛函理论 (DFT) 计算得到进一步验证，表明其对 TcO _{4的独特化学识别}^——优于其他具有更高电荷密度的阴离子。