ZIF-L membrane with a membrane-interlocked-support composite architecture for H/CO separation  

具有膜-载体互锁型复合微结构的ZIF-L膜应用于H_(2)/CO_(2)分离

作　　者：Kun Yang Sulei Hu Yujie Ban Yingwu Zhou Na Cao Meng Zhao Yifei Xiao Weixue Li Weishen Yang 杨昆;胡素磊;班宇杰;周应武;曹娜;赵萌;肖依非;李微雪;杨维慎(State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China;Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei 230026,China;University of Chinese Academy of Sciences,Beijing 100039,China;Department of Chemical Physics,School of Chemistry and Materials Science,iCHeM,Chinese Academy of Sciences,Excellence Center for Nanoscience,University of Science and Technology of China,Hefei 230026,China;Dalian National Laboratory for Clean Energy,Dalian 116023,China)

机构地区：[1]State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [2]Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei 230026,China [3]University of Chinese Academy of Sciences,Beijing 100039,China [4]Department of Chemical Physics,School of Chemistry and Materials Science,iCHeM,Chinese Academy of Sciences,Excellence Center for Nanoscience,University of Science and Technology of China,Hefei 230026,China [5]Dalian National Laboratory for Clean Energy,Dalian 116023,China

出　　处：《Science Bulletin》2021年第18期1869-1876,M0003,M0004,共10页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(21978283,22090060,and 22090063);the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17020400);Liaoning Revitalization Talents Program(XLYC1801004);the DNL Cooperation Fund,Chinese Academy of Sciences(DNL201920);Youth Innovation Promotion Association of Chinese Academy of Sciences,and Dalian Institute of Chemical Physics(DICP ZZBS201711);the financial support of National Key R&D Program of China(2018YFA0208603);K.C.Wong Education Foundation(GJTD-2020-15)。

摘　　要：Metal–organic framework(MOF)membranes hold great promise in energy-efficient chemical separations.The outstanding challenges of the microstructural design stem from(1)thinning of membranes to immensely reduce the mass-transfer resistance(for high permeances);(2)tuning of orientation to optimize the selective transport of gas molecules,and(3)reinforcement of intercrystalline structure to subside leakage through defective gaps(for high selectivity).Here,we propose the ZIF-L membrane that is completely confined into the voids of the alumina support through an interfacial assembly process,producing an appealing membrane-interlocked-support(MIS)composite architecture that meets the requirements of the microstructural design of MOF membranes.Consequently,the membranes show average H2 permeances of above 4000 GPU and H_(2)/CO_(2) separation factor(SF)of above 200,representing record-high separation performances of ZIF-L membranes and falling into the industrial target zone(H_(2) permeance>1000 GPU and H_(2)/CO_(2) SF>60).Furthermore,the ZIF-L membrane possessing the MIS composite architecture that is established with alumina particles as scaffolds shows mechanical stability,scraped repeatedly by a piece of silicon rubber causing no selectivity loss.金属-有机骨架(MOF)膜在低能耗化工分离领域具有广阔应用前景.其关键在于膜的微结构设计,所面临重要挑战有:(1)如何降低膜层厚度以极大减小传质阻力;(2)如何调控膜的孔道取向以优化分子选择性传输;(3)如何强化晶界结构以最大程度减少缺陷流,进而实现高渗透率和高分离选择性.本文利用原位界面组装策略制备ZIF-L膜.通过调变配体浓度,可将膜层完全限制在载体孔隙内,形成高度取向的膜-载体互锁型复合微结构,膜表观厚度为零,充分满足了上述设计原则.ZIF-L膜的气体测试结果显示,其H_(2)/CO_(2)分离因子超过200,H_(2)渗透率达4000 GPU以上,性能位于工业应用目标区域(H_(2)渗透率>1000 GPU,H_(2)/CO_(2)分离因子>60),为迄今H_(2)/CO_(2)分离性能最优的ZIF-L膜.再者,这种具有膜-载体互锁型复合微结构的ZIF-L膜,展现出良好的机械稳定性.以硅橡胶垫反复刮擦膜表面,不会造成选择性下降.这为MOF膜的微结构设计提供了重要方向.

关 键 词：MOF membranes Membrane-interlocked-support composite ARCHITECTURE H_(2)/CO_(2)separation Interfacial assembly 

分 类 号：TQ051.893[化学工程]