膜科学与技术

机械化学法合成多配体MOF填料用于高效CO2分离

作者：赵新，乔志华，孙玉绣，郭翔宇，仲崇立

单位：天津工业大学省部共建分离膜与膜过程国家重点实验室，化学工程与技术学院，天津 300387

关键词：机械化学法；ZIF-8-Bim-Ica；多配体；混合基质膜；CO2分离

出版年,卷(期):页码： 2021,41(5):11-16

摘要：

以ZIF-8为母体材料通过机械化学手段引入苯并咪唑（Bim）和咪唑-2-甲醛（Ica）两种配体，得到多配体的MOF材料ZIF-8-Bim-Ica。与聚醚共聚酰胺（Pebax-1657）混合制得混合基质膜（MMMs）。利用XRD、FT-IR、核磁共振氢谱等方法确定了ZIF-8-Bim-Ica的化学结构，利用SEM对混合基质膜的断面进行表征。结果表明，引入Bim和Ica配体后，ZIF-8的结构没有被破坏，ZIF-8-Bim-Ica颗粒均匀分散于Pebax聚合物中。加入ZIF-8-Bim-Ica提高了混合基质膜的CO2渗透通量和对CO2/CH4的选择性。与纯膜相比,掺杂量为10 wt%时，混合基质膜的CO2渗透通量可达269.3 Barrer，提高了29.3 %，CO2/CH4的选择性由18.5提高到43.8，并且膜性能至少可保持40 h的稳定性。由本方法制备的ZIF-8-Bim-Ica/Pebax混合基质膜对CO2的选择性较高，在CO2气体分离领域展现出良好的应用前景。

ZIF-8 was synthesized by mechanization method. With ZIF-8 as the parent，the mixed ligands MOF material ZIF-8-Bim-Ica was obtained by mechanochemical means to introduce benzimidazole (Bim) and 2-Imidazolecarboxaldehyde (Ica). Mixed matrix membranes (MMMS) was prepared by mixing with polyether copolyamide (Pebax-1657). The chemical structure of ZIF-8-Bim-Ica was determined by XRD，FTIR and 1H NMR spectra，and the cross section of the mixed matrix membranes were characterized by SEM. The results showed that the structure of ZIF-8 was not damaged after the introduction of Bim and Ica, and the ZIF-8-Bim-Ica particles were evenly dispersed in the Pebax polymer. The addition of ZIF-8-Bim-Ica improved the CO2 permeation flux and the CO2/CH4 selectivity of the mixed matrix membranes. Compared with the pure membrane，the CO2 permeation flux of the mixed matrix membrane with 10 wt% doping amount can reach 269.3 Barrer，increased by 29.3 %，and the CO2/CH4 selectivity is increased from 18.5 to 43.8，and the stability of the membrane can be maintained for at least 40 hours. The ZIF-8-Bim-Ica/Pebax mixed matrix membranes prepared by this method has a high selectivity to CO2，showing a good application prospect in the field of CO2 gas separation.

赵新（1995-），男，河北衡水人，硕士研究生，主要研究方向为气体分离膜的制备，Email：zhaoxintgd@163.com

参考文献：

[1] Dong G，Li H，Chen V. Challenges and opportunities for mixed-matrix membranes for gas separation[J]. J. Mater. Chem. A，2013，1: 4610-4630 .
[2] Goh P S，Ismail A F，Sanip S M，et al. Recent advances of inorganic fillers in mixed matrix membrane for gas separation[J]. Separation and Purification Technology，2011，3(81): 243-264.
[3] Wang H，He S，Qin X，et al. Interfacial Engineering in Metal-Organic Framework-Based Mixed Matrix Membranes Using Covalently Grafted Polyimide Brushes[J]. J. Am. Chem. Soc，2018，140(49): 17203–17210.
[4] Denny M S，Cohen S M. In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes[J]. Angewandte Chemie，2015，127(31): 9157-9160.
[5] Chung T S，Jiang L，Li Y，et al. Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation[J]. Progress in Polymer Science，2007，32(4): 483-507.
[6] Furukawa H，Cordova K E，et al. The chemistry and applications of metal-organic frameworks[J]. Science，2013，341(6149): 974.
[7] Hillman F，Brito J，et al. Rapid One-Pot Microwave Synthesis of Mixed-Linker Hybrid Zeolitic-Imidazolate Framework Membranes for Tunable Gas Separations[J]. ACS Applied Materials & Interfaces，2018，10(6): 5586-5593.
[8] Hillman F，Jeong H K. Linker-doped Zeolitic-Imidazolate Frameworks (ZIFs) and their Ultrathin Membranes for Tunable Gas Separations[J]. ACS Applied Materials & Interfaces，2019，11(20): 18377-18385.
[9] Hu C，Lin C，Chiao Y，et al. The Mixing Effect of Ligand on Carbon Dioxide Capture Behavior of Zeolitic Imidazolate Framework/Poly (amide-b-ethylene oxide) Mixed Matrix Membranes[J]. ACS Sustainable Chemistry & Engineering，2018，6(11): 15341-15348.
[10] Thompson J A，Vaughn J T，Brunelli N A，et al. Mixed-linker zeolitic imidazolate framework mixed-matrix membranes for aggressive CO2 separation from natural gas[J]. Microporous & Mesoporous Materials，2014，192: 43-51.
[11] Eum K，Rashidi F，et al. Highly tunable molecular sieving and adsorption properties of mixed-linker zeolitic imidazolate frameworks.[J]. Journal of the American Chemical Society，2015，137(12): 4191-4197.
[12] Zhang C，Xiao Y，Liu D，et al. A hybrid zeolitic imidazolate framework membrane by mixed-linker synthesis for efficient CO2 capture[J]. Chemical Communications，2012，49(6): 600-602.
[13] Hou Q，Wu Y，Zhou S，et al. Ultra-Tuning of the Aperture Size in Stiffened ZIF-8_Cm Frameworks with Mixed-Linker Strategy for Enhanced CO2/CH4 Separation[J]. Angewandte Chemie International Edition，2018，58(1): 327-331.
[14] Banerjee R，Phan A，Wang B，et al. High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture[J]. Science，2008，319(5865): 939-943.
[15] Banerjee R，Furukawa H，et al. Control of pore size and functionality in isoreticular zeolitic imidazolate frameworks and their carbon dioxide selective capture properties.[J]. Journal of the American Chemical Society，2009，131(11): 3875.
[16] Karagiaridi O，Bury W，Sarjeant A A，et al. Synthesis and characterization of isostructural cadmium zeolitic imidazolate frameworks via solvent-assisted linker exchange[J]. Chemical Science，2012，3(11): 3256.
[17] Thompson J A，Blad C R，Brunelli N，et al. Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by Mixed-Linker Synthesis[J]. Chemistry of Materials，2012，24(10): 1930–1936.
[18] Huang Y，Lo W，Kuo Y，et al. Green and rapid synthesis of zirconium metal–organic frameworks via mechanochemistry: UiO-66 analog nanocrystals obtained in one hundred seconds[J]. Chemical Communications，2017，53: 5818-5821.
[19] Batista M M，Luque R，et al. Mechanochemistry: Toward Sustainable Design of Advanced Nanomaterials for Electrochemical Energy Storage and Catalytic Applications[J]. ACS Sustainable Chemistry & Engineering，2018，6(8): 9530-9544.
[20] Do J L，Friscic T. Mechanochemistry: A Force of Synthesis[J]. ACS Cent Sci，2017，3(1): 13-19.
[21] Zhou X，Miao Y，Suslick K S，et al. Mechanochemistry of Metal-Organic Frameworks Under Pressure and Shock[J]. Accounts of Chemical Research，2020，53(12): 2806-2815.
[22] 王树清，乔志华，王志. 分离CO2固定载体膜工业化制备技术[J]. 膜科学与技术，2016，36(5): 87-94.
[23] 王树清，乔志华，王志. 以3-甲氧基苄胺改性聚乙烯基胺制备CO2分离膜[J]. 膜科学与技术，2016，36(3): 1-7.
[24] 曹晓畅，王志，乔志华，等. 一步法制备含氨基化合物的非对称CO2分离膜[J]. 化工学报，2018，69(11):4778-4787.
[25] 何玉鹏，王志，乔志华，等. 含有MCM-41分子筛的混合基质复合膜用于CO2分离[J]. 化工学报，2015，66(10):3979-3990.
[26] 瞿媛媛，张玉龙，张丛健，等. 改善MOFs/聚合物混合基质膜气体分离性能的策略[J]. 膜科学与技术，2019，39(2): 135-142.
[27] 田洋洋，梁家晨，沈钦，等. MOF基混合基质膜的界面设计及气体分离研究进展[J]. 膜科学与技术，2019，39(1):129-139.
[28] 郭翔宇，阳庆元，含开放金属位点MIL-101(Cr)掺杂的混合基质膜制备及其CO2分离性能[J]. 化工学报，2017，68(11): 4323-4332.
[29] Guo X，Huang H，Ban Y，et al. Mixed matrix membranes incorporated with amine-functionalized titanium-based metal-organic framework for CO2/CH4 separation[J]. J Membr Sci，2015，478: 130-139.
[30] Jomekian A，Kargari A，et al. Utilization of Pebax 1657 as structure directing agent in fabrication of ultra-porous ZIF-8[J]. Journal of Solid State Chemistry，2016，236: 212-216.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com