Cheng Zeliang, Zhang Pinyue, Wang Ziyang, Jiang Haicheng, Wang Wenjian, Liu Dandan, Wang Lina, Zhu Guangshan, Zou Xiaoqin
Faculty of Chemistry, Northeast Normal University, Changchun, 130024, P. R. China.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P. R. China.
Small. 2023 Jul;19(30):e2300438. doi: 10.1002/smll.202300438. Epub 2023 Apr 8.
Covalent organic frameworks (COFs) mixed matrix membranes (MMMs) combining individual attributes of COFs and polymers are promising for gas separation. However, applying COF MMMs for propylene/propane (C H /C H ) separation remains a big challenge due to COF inert pores and C H /C H similar molecular sizes. Herein, the designed synthesis of a Cu(I) coordinated COF for membrane C H /C H separation is reported. A platform COF is synthesized from 5,5'-diamino-2,2'-bipyridine and 2-hydroxybenzene-1,3,5-tricarbaldehyde. This COF possesses a porous 2D structure with high crystallinity. Cu(I) is coordinated to bipyridyl moieties in the COF framework, acting as recognizable sites for C H gas, as shown by the adsorption measurements. Cu(I) COF is blended with 6FDA-DAM polymer to yield MMMs. This COF MMM exhibits selective and permeable separation of C H from C H (C H permeability of 44.7 barrer, C H /C H selectivity of 28.1). The high porosity and Cu(I) species contribute to the great improvement of separation performance by virtue of 2.3-fold increase in permeability and 2.2-fold increase in selectivity compared to pure 6FDA-DAM. The superior performance to those of most relevant reported MMMs demonstrates that the Cu(I) coordinated COF is an excellent candidate material for C H separation membranes.
共价有机框架(COF)混合基质膜(MMM)结合了COF和聚合物的各自特性,在气体分离方面颇具前景。然而,由于COF的惰性孔隙以及丙烯/丙烷(C₃H₆/C₃H₈)相似的分子尺寸,将COF MMM应用于丙烯/丙烷分离仍然是一个巨大的挑战。在此,报道了一种用于膜丙烯/丙烷分离的Cu(I)配位COF的设计合成。一种平台COF由5,5'-二氨基-2,2'-联吡啶和2-羟基苯-1,3,5-三甲醛合成。这种COF具有高结晶度的多孔二维结构。如吸附测量所示,Cu(I)在COF框架中与联吡啶部分配位,作为C₃H₆气体的可识别位点。将Cu(I)COF与6FDA-DAM聚合物共混以制备MMM。这种COF MMM表现出对C₃H₆与C₃H₈的选择性和渗透性分离(C₃H₆渗透率为44.7巴每尔,C₃H₆/C₃H₈选择性为28.1)。与纯6FDA-DAM相比,高孔隙率和Cu(I)物种使分离性能得到显著改善,渗透率提高了2.3倍,选择性提高了2.2倍。与大多数相关报道的MMM相比,其优异的性能表明Cu(I)配位COF是一种用于C₃H₆分离膜的优秀候选材料。