Highly conductive and robust composite anion exchange membranes by incorporating quaternized MIL-101(Cr)  

作　　者：Xueyi He Mingyue Gang Zhen Li Guangwei He Yongheng Yin Li Cao Bei Zhang Hong Wu Zhongyi Jiang 

机构地区：[1]Key Laboratory for Green Technology of Ministry of Education,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China [2]Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300072,China [3]Institute of Nuclear and New Energy Technology,Tsinghua University,Beijing 100084,China

出　　处：《Science Bulletin》2017年第4期266-276,共11页科学通报（英文版）

基　　金：supported by the National Science Fund for Distinguished Young Scholars(21125627);the National Natural Science Founds of China(21490583 and 21621004);the Program of Introducing Talents of Discipline to Universities(B06006).

摘　　要：With well-defined channels and tunable functionality, metal-organic frameworks （MOFs） have inspired the design of a new class of ion-conductive compounds. In contrast to the extensive studies on proton- conductive MOFs and related membranes attractive for fuel cells, rare reports focus on MOFs in preparation of anion exchange membranes. In this study, chloromethylated MIL-101 （Cr） was prepared and incor- porated into chloromethylated poly （ether ether ketone） （PEEK） as a multifunctional filler to prepare imidazolium PEEK/imidazolium MIL-101（Cr） （ImPEEK/ImMIL-101（Cr）） anion exchange membrane after synchronous quaternization. The successful synthesis and chloromethylation of MIL-101（Cr） were veri- fied by transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy while the enhanced performance of composite membranes in hydroxide conductivity, mechanical strength and dimensional stability were evaluated by alternating-current impedance, electronic stretching machine and measurement of swelling ratio. Specifically, incorporating 5.0wt% ImMIL-101（Cr） afforded a 71.4% increase in hydroxide conductivity at 20℃, 100% RH. Besides, the composite membranes exhibited enhanced dimensional stability and mechanical strength due to the rigid framework of ImMIL- 101（Cr）. At room temperature and the ImM1L-101（Cr） content of 10wt%, the swelling ratio of the ImPEEK/lmMIL-101（Cr） was 70.04% lower while the tensile strength was 47.5% higher than that of the pure membrane.With well-defined channels and tunable functionality, metal-organic frameworks(MOFs) have inspired the design of a new class of ion-conductive compounds. In contrast to the extensive studies on protonconductive MOFs and related membranes attractive for fuel cells, rare reports focus on MOFs in preparation of anion exchange membranes. In this study, chloromethylated MIL-101(Cr) was prepared and incorporated into chloromethylated poly(ether ether ketone)(PEEK) as a multifunctional filler to prepare imidazolium PEEK/imidazolium MIL-101(Cr)(Im PEEK/Im MIL-101(Cr)) anion exchange membrane after synchronous quaternization. The successful synthesis and chloromethylation of MIL-101(Cr) were verified by transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy while the enhanced performance of composite membranes in hydroxide conductivity, mechanical strength and dimensional stability were evaluated by alternating-current impedance, electronic stretching machine and measurement of swelling ratio. Specifically, incorporating 5.0 wt% Im MIL-101(Cr)afforded a 71.4% increase in hydroxide conductivity at 20 °C, 100% RH. Besides, the composite membranes exhibited enhanced dimensional stability and mechanical strength due to the rigid framework of Im MIL-101(Cr). At room temperature and the Im MIL-101(Cr) content of 10 wt%, the swelling ratio of the Im PEEK/Im MIL-101(Cr) was 70.04% lower while the tensile strength was 47.5% higher than that of the pure membrane.

关 键 词：MIL-101（Cr）Poly （ether ether ketone） Chloromethylation Quaternization Composite anion exchange membranes 

分 类 号：TQ425.236[化学工程] O641.4[理学—物理化学]