Zheng Zhaoqi, Hong Yan, Zheng Peixu, Luo Wei, Qiu Jianhua, Jiang Liping
School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin, 541004, China.
College of Environment and Resources, Guangxi Normal University, Guilin, 541004, China.
Chemistry. 2025 Jun 26;31(36):e202500546. doi: 10.1002/chem.202500546. Epub 2025 May 27.
The development of highly efficient materials for trapping radioactive iodine is essential for the safe use of nuclear energy. Herein, we present a strategy to synergistically enhance iodine capture by exploiting the flexible building blocks with the affinity properties of electrically rich heteroatoms by combining the cyclic triphosphonitrile derivative with amine linkers of different molecular lengths and constructing triangular pore-structured flexible cyclotriphosphonitrile-based covalent organic frameworks. A series of cyclotriphosphonitrile-based COFs (CTP-X-COF, X = PDA, ODA, BPY, DPT) with triangular pore topology were synthesized using CTP-6 as the node and connection point of p-phenylenediamine (PDA), 4,4-diaminodiphenyl ether (ODA), 5,5-diamino2,2-bipyridine (BPY), and 4,4-diaminotribiphenyl (DPT) with different molecular lengths. It was found that the adsorption capacities of CTP-PDA-COF, CTP-ODA-COF, CTP-BPY-COF, and CTP-DPT-COF for iodine vapor were 4.65 g g, 4.18 g g, 2.38 g g, and 3.57 g g, respectively. The results showed that the adsorption capacities of CTP-PDA-COF, CTP-ODA-COF, CTP-BPY-COF, and CTP-DPT-COF for iodine in cyclohexane were 281.50 mg g, 221.67 mg g, 161.14 mg g, and 222.67 mg g, respectively. It was found that the four COFs adsorbed iodine in cyclohexane solution was a mixed adsorption process with chemical adsorption playing a predominant role and physical adsorption as an auxiliary mechanism.
开发高效的放射性碘捕获材料对于核能的安全使用至关重要。在此,我们提出了一种策略,通过将环状三膦腈衍生物与不同分子长度的胺连接体相结合,并构建具有三角形孔结构的柔性环三膦腈基共价有机框架,利用富含电子的杂原子的亲和特性来协同增强碘捕获。使用CTP-6作为对苯二胺(PDA)、4,4'-二氨基二苯醚(ODA)、5,5'-二氨基-2,2'-联吡啶(BPY)和4,4'-二氨基三联苯(DPT)的节点和连接点,合成了一系列具有三角形孔拓扑结构的环三膦腈基共价有机框架(CTP-X-COF,X = PDA、ODA、BPY、DPT)。结果发现,CTP-PDA-COF、CTP-ODA-COF、CTP-BPY-COF和CTP-DPT-COF对碘蒸气的吸附容量分别为4.65 g/g、4.18 g/g、2.38 g/g和3.57 g/g。结果表明,CTP-PDA-COF、CTP-ODA-COF、CTP-BPY-COF和CTP-DPT-COF在环己烷中对碘的吸附容量分别为281.50 mg/g、221.67 mg/g、161.14 mg/g和222.67 mg/g。研究发现,这四种共价有机框架在环己烷溶液中吸附碘是一个混合吸附过程,其中化学吸附起主要作用,物理吸附为辅助机制。