Dong Junchao, Gai Dongxu, Cha Guocai, Pan Qinhe, Liu Jia, Zou Xiaoqin, Zhu Guangshan
Faculty of Chemistry, Northeast Normal University Changchun 130024 China
College of Chemistry, Jilin University Changchun 130012 China.
Chem Sci. 2024 Oct 28;15(45):19013-21. doi: 10.1039/d4sc05080k.
Metal organic cages (MOCs) show promise as fillers in mixed-matrix membranes (MMMs) for gas separation; highly soluble MOCs are desirable for fabrication of high-compatibility membranes. Herein, we report an iodine substitution strategy to substantially increase the MOC solubility. The synthesized MOC of ZrT-NH-I possesses over 10-fold higher solubility than the parent ZrT-NH in organic solvents whilst retaining the original molecular structure and permanent porosity. Such enhanced solubility allows for the effective integration of ZrT-NH-I with an amidoxime polymer of intrinsic microporosity (PIM-PAO), resulting in a compatible MMM with a uniform distribution of MOC. The ZrT-NH-I@PIM-PAO MMM demonstrates a CO permeability of 1377 barrer and a CO/N gas selectivity of 45 which is 45 times that of the membrane made from ZrT-NH. The permeability-selectivity performance not only surpasses the 2008 upper bound, but also exceeds those of currently available MMMs.
金属有机笼（MOCs）作为混合基质膜（MMMs）中的气体分离填料具有应用前景；高溶解性的MOCs对于制备高相容性膜是理想的。在此，我们报道一种碘取代策略以大幅提高MOC的溶解度。合成的ZrT-NH-I金属有机笼在有机溶剂中的溶解度比母体ZrT-NH高10倍以上，同时保留了原始分子结构和永久孔隙率。这种增强的溶解度使得ZrT-NH-I能够与具有固有微孔性的偕胺肟聚合物（PIM-PAO）有效结合，从而得到一种MOC分布均匀的相容性混合基质膜。ZrT-NH-I@PIM-PAO混合基质膜的CO渗透率为1377巴耳，CO/N2气体选择性为45，是由ZrT-NH制成的膜的45倍。其渗透选择性性能不仅超过了2008年的上限，也超过了目前可用的混合基质膜。
