De novo synthesis of bifunctional conjugated microporous polymers for synergistic coordination mediated uranium entrapment
De novo synthesis of bifunctional conjugated microporous polymers for synergistic coordination mediated uranium entrapment
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用于协同配位介导铀捕获的双功能共轭微孔聚合物的从头合成
DOI：
10.1007/s12274-020-3217-7
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发表时间：
2020-11
期刊：
影响因子：
9.9
通讯作者：
Ma Shengqian
中科院分区：
文献类型：
--
作者：
Yu Boxuan;Zhang Lei;Ye Gang;Liu Qingzhi;Li Jiongli;Wang Xudong;Chen Jing;Xu Shengming;Ma Shengqian
本工作报道了一种新的双功能共轭微孔聚合物（CMP）的从头合成，表现出协同效应涉及铀的配位行为。强调的是，合成策略使得能够通过特异性地引入邻位取代的氨基官能团来工程化偕胺肟官能化CMP框架内的配位环境，通过形成协同配合物来增强对铀酰离子的亲和力。CMP表现出高的Brunauer-Emmett-Teller（BET）表面积、具有分级多孔性的发达的三维（3D）网络以及由于共价交联结构而具有的有利的化学和热稳定性。与无氨基化合物相比，双功能化合物对铀的吸附容量从105 mg/g增加到174 mg/g，提高了近70%，表明其对铀的结合能力明显增强。此外，通过X射线光电子能谱（XPS）和密度泛函理论（DFT）计算，对配位机理有了新的认识，表明肟配体与铀酰离子形成1：1的金属离子/配体（M/L）配位模型，同时表明氨基官能团通过直接与铀中心结合和氢键参与次级球相互作用而协同作用.这一工作揭示了邻位取代官能团协同作用促进偕胺肟与铀酰离子配位的基本原理。本文所建立的合成策略将有助于开发更多具有特定用途的新型CMP基功能材料，以拓宽其应用领域。
This work reports a de novo synthesis of novel bifunctional conjugated microporous polymers (CMPs) exhibiting a synergistic-effect involved coordination behavior to uranium. It is highlighted that the synthetic strategy enables the engineering of the coordination environment within amidoxime functionalized CMP frameworks by specifically introducing ortho -substituted amino functionalities, enhancing the affinity to uranyl ions via forming synergistic complexes. The CMPs exhibit high Brunauer-Emmett-Teller (BET) surface area, well-developed three-dimensional (3D) networks with hierarchical porosity, and favorable chemical and thermal stability because of the covalently cross-linked structure. Compared with the amino-free counterparts, the adsorption capacity of bifunctional CMPs was increased by almost 70%, from 105 to 174 mg/g, indicating evidently enhanced binding ability to uranium. Moreover, new insights into coordination mechanism were obtained by in-depth X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculation, suggesting a dominant role of the oxime ligands forming a 1:1 metal ions/ligands (M/L) coordination model with uranyl ions while demonstrating the synergistic engagement of the amino functionalities via direct binding to uranium center and hydrogen-bonding involved secondary-sphere interaction. This work sheds light on the underlying principles of ortho-substituted functionalities directed synergistic effect to promote the coordination of amidoxime with uranyl ions. And the synthetic strategy established here would enable the task-specific development of more novel CMP-based functional materials for broadened applications.
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