Thiophene-based conjugated ultra-micropore rigid polymers for selective xenon capture
Thiophene-based conjugated ultra-micropore rigid polymers for selective xenon capture
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用于选择性氙捕获的噻吩基共轭超微孔刚性聚合物
DOI：
10.1016/j.cej.2022.139934
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发表时间：
2022
影响因子：
15.1
通讯作者：
Chuanqin Xia
中科院分区：
文献类型：
--
作者：
Zijun Yan;Yu Luo;Bo Chen;Fenglei Wang;Lang Chen;Zining Wang;Pengwei Zhao;Jinyang Kang;Zhihai Fu;Yongdong Jin;None YuanhuaWang;Chuanqin Xia
噻吩基CMP-PY-TBTP由于S原子对Kr的高极化性，对Kr具有较强的相互作用和较高的Kr/Kr选择性。·以高产率合成了三种基于噻吩的刚性CMP。·刚性噻吩的极化和噻吩限制有助于噻吩/Kr选择性。·基于噻吩的刚性CMP表现出很大的热稳定性和酸/碱稳定性。氪（Kr）和氙（Xe）的放射性同位素是由核反应堆的裂变反应产生的。从核尾气中分离出氘/氪是乏燃料后处理的重要环节。与工业上常用的低温精馏方法相比，物理吸附法是一种简单、节能的分离氘/氪的方法。本文通过直接C-H芳基化反应，高产率地合成了含噻吩的CMP-PY-BTP、TBTP和含氟的CMP-PY-TFB三种刚性共轭嵌段聚合物，并描述了它们与嵌段/Kr分离的结构-功能关系。CMP-PY-TFB、BTP和TBTP都具有刚性微孔，其比表面积分别为786.25、141.64和488.30 m 2 g −1。在三种聚合物中，CMP-PY-TBTP表现出最高的噻吩/氪选择性（理想吸附溶液理论选择性为11.9，亨利选择性为9.3），这是由于其噻吩结构单元的较强极化和噻吩限制（5.4 π）的综合作用。密度泛函理论（DFT）计算结果表明，噻吩基的吸附比含氟基的吸附更强，说明噻吩基的极化导致了更强的相互作用。含氟的CMP-PY-TFB虽然对γ-Al 2 O3的极化较弱，但由于其最大的比表面积（786.25 m2 g −1），其γ-Al 2 O3吸收率最高，为43.59 cm 3 g −1。
Due to S atom’s high polarization to Xe, thiophene-based CMP-PY-TBTP exhibited strong interaction to Xe and high Xe/Kr selectivity. • Three thiophene-based rigid CMPs were synthesized in high yield. • Polarization of rigid thiophene and micropore confinement contributed to Xe/Kr selectivity. • The thiophene-based rigid CMPs exhibited great thermal and acid/base stability. Radioactive isotopes of krypton (Kr) and xenon (Xe) are produced from the fission reaction of nuclear reactors. The separation of Xe/Kr from the nuclear off-gas is important for the spent fuel reprocessing. Compared with the industrial method of cryogenic distillation, physical adsorption is a simple and energy-saving method for Xe/Kr separation. Here, three rigid conjugated micropore polymers, including thiophene containing CMP-PY-BTP, TBTP and fluorine-containing CMP-PY-TFB, were prepared in high yield through direct C-H arylation reaction, and their structure-function relationship with Xe/Kr separation was described. CMP-PY-TFB, BTP, and TBTP all possessed rigid micropores with Brunauer-Emmett-Teller specific surface areas of 786.25, 141.64 and 488.30 m 2 g −1 , respectively. Among three polymers, CMP-PY-TBTP exhibited the highest Xe/Kr selectivity (11.9 for ideal adsorption solution theory selectivity and 9.3 for Henry selectivity), owing to the combined effect of stronger polarization of its thiophene structural unit and micropore confinement (5.4 Å). The density functional theory (DFT) calculation revealed that Xe was more strongly adsorbed in thiophene-containing units than that of fluorine-containing unit which verified the stronger interaction caused by thiophene group’s polarization. Though having weaker polarization to Xe, fluorine-containing CMP-PY-TFB exhibited the highest Xe uptake of 43.59 cm 3 g −1 due to its largest specific surface area (786.25 m 2 g −1 ).