金属有机骨架/聚酰胺薄层纳米复合膜的研究进展

doi:10.16085/j.issn.1000-6613.2021-1946

摘要/Abstract

摘要：

相较于传统聚酰胺薄层复合（TFC）膜，金属有机骨架/聚酰胺薄层纳米复合（TFN）膜得益于MOFs材料的高比表面积、有序可控的孔隙结构、良好的聚合物相容性和可定制的化学功能，展现出更高的渗透选择性，在工业应用中显示出巨大的分子和离子分离潜力。本文首先简述了MOFs聚酰胺复合膜的研究背景，然后从MOFs材料的特性和MOFs聚酰胺复合膜的制备策略两个方面出发，总结了MOFs聚酰胺膜研究的最新进展。讨论了MOFs的物化特征在TFN膜的微观结构和分离性能中起的作用；介绍了MOFs聚酰胺复合膜的制备策略，重点对MOFs负载方法及效率进行了分析。最后简述了MOFs聚酰胺复合膜在气、液体系分离中的应用；对MOFs聚酰胺膜在应用过程中的稳定性问题进行了分析，并对未来MOFs聚酰胺复合膜优化MOFs负载和功能性设计的研究进行了展望。

关键词: 金属有机骨架, 薄层纳米复合膜, 制备策略, 膜分离

Abstract:

Compared to the traditional polyamide thin-film composite (TFC) membranes, metal-organic frameworks (MOFs)/polyamide thin-film nanocomposite (TFN) membranes exhibit higher perm-selectivity and show great potential for molecular and ion separation in industrial applications, which benefited from MOFs materials with high surface area, orderly and controllable pore structure, favored polymer affinity and customizable chemical function. This review first briefly introduced the research background of MOFs polyamide composite membrane, and then summarized the progress of MOFs polyamide composite membrane in terms of the characteristics of MOFs materials and the preparation strategy of MOFs polyamide composite membrane. The roles of physicochemical features of MOFs in the microstructure and separation performance of TFN membranes are discussed. Subsequently, various preparation strategies of MOFs doped polyamide membrane are introduced, and the loading efficiency of MOFs is analyzed. Finally, the application of MOFs polyamide composite membrane in gas and liquid system separation is briefly described. The stability of MOFs polyamide membrane in the application process is analyzed, and the future research of MOFs polyamide composite membrane in the optimization of MOFs load and functional design is prospected.

Key words: metal-organic frameworks (MOFs), thin-film nanocomposite membranes, preparation strategies, membrane separation

中图分类号:

TQ028.8

朱晓, 朱军勇, 张亚涛. 金属有机骨架/聚酰胺薄层纳米复合膜的研究进展[J]. 化工进展, 2022, 41(8): 4314-4326.

ZHU Xiao, ZHU Junyong, ZHANG Yatao. Research progress of metal organic framework/polyamide thin film nanocomposite membrane[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4314-4326.

图/表 6

图1 2008—2021年发表有关水稳定性MOFs和MOFs-TFN膜的文章数量统计

图2 典型MOFs的酸碱稳定性绿色—MOFs能承受的pH范围；黄色和紫色—MOFs不能承受的过酸过碱pH范围

图3 MOFs荷电性在TFN制备和应用中的作用

图4 真空辅助过滤法制备TFN膜

图5 ZIF-8@ZNPM的制备过程示意图

图6 蒸发控制填料定位（EFP）制备TFN膜上图—EFP法的具体过程；下图—传统界面聚合过程

参考文献 65

1	SHANNON M A, BOHN P W, ELIMELECH M, et al. Science and technology for water purification in the coming decades[J]. Nature, 2008, 452(7185): 301-310.
2	JI C H, ZHAI Z, JIANG C, et al. Recent advances in high-performance TFC membranes: a review of the functional interlayers[J]. Desalination, 2021, 500: 114869.
3	秘一芳, 安全福. 界面聚合聚酰胺纳滤膜渗透选择性能优化的研究进展[J]. 化工进展, 2020, 39(6): 2093-2104.
	MI Yifang, AN quanfu. Progress in optimization of polyamide nanofiltration membranes prepared by interfacial polymerization for perm-selectivity[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2093-2104.
4	LI D, YAN Y S, WANG H T. Recent advances in polymer and polymer composite membranes for reverse and forward osmosis processes[J]. Progress in Polymer Science, 2016, 61: 104-155.
5	ZHU Y, DOU P J, HE H L, et al. Improvement of permeability and rejection of an acid resistant polysulfonamide thin-film composite nanofiltration membrane by a sulfonated poly(ether ether ketone) interlayer[J]. Separation and Purification Technology, 2020, 239: 116528.
6	LEE T H, OH J Y, HONG S P, et al. ZIF-8 particle size effects on reverse osmosis performance of polyamide thin-film nanocomposite membranes: importance of particle deposition[J]. Journal of Membrane Science, 2019, 570/571: 23-33.
7	LAU W J, GRAY S, MATSUURA T, et al. A review on polyamide thin film nanocomposite (TFN) membranes: history, applications, challenges and approaches[J]. Water Research, 2015, 80: 306-324.
8	姜蕾, 张大鹏, 朱桂茹, 等. Zr-MOFs改性聚酰胺正渗透复合膜的制备与表征[J]. 功能材料, 2017, 48(3): 3102-3107.
	JIANG Lei, ZHANG Dapeng, ZHU Guiru, et al. Fabrication and characterization of Zr-MOFs incorporated thin-film nanocomposite membrane for forward osmosis[J]. Jorunal of Functional Materials, 2017, 48(3): 3102-3107.
9	JEONG B H, HOEK E M V, YAN Y S, et al. Interfacial polymerization of thin film nanocomposites: a new concept for reverse osmosis membranes[J]. Journal of Membrane Science, 2007, 294(1/2): 1-7.
10	GHANBARI M, EMADZADEH D, LAU W J, et al. Synthesis and characterization of novel thin film nanocomposite (TFN) membranes embedded with halloysite nanotubes (HNTs) for water desalination[J]. Desalination, 2015, 358: 33-41.
11	NIKSEFAT N, JAHANSHAHI M, RAHIMPOUR A. The effect of SiO₂ nanoparticles on morphology and performance of thin film composite membranes for forward osmosis application[J]. Desalination, 2014, 343: 140-146.
12	JI C H, XUE S M, TANG Y J, et al. Polyamide membranes with net-like nanostructures induced by different charged MOFs for elevated nanofiltration[J]. ACS Applied Polymer Materials, 2019, 2(2): 585-593.
13	BÉTARD A, FISCHER R A. Metal-organic framework thin films: from fundamentals to applications[J]. Chemical Reviews, 2012, 112(2): 1055-1083.
14	HE Y R, TANG Y P, MA D C, et al. UiO-66 incorporated thin-film nanocomposite membranes for efficient selenium and arsenic removal[J]. Journal of Membrane Science, 2017, 541: 262-270.
15	KADHOM M, HU W M, DENG B L. Thin film nanocomposite membrane filled with metal-organic frameworks UiO-66 and MIL-125 nanoparticles for water desalination[J]. Membranes, 2017, 7(2): E31.
16	WANG C H, LIU X L, KESER DEMIR N, et al. Applications of water stable metal-organic frameworks[J]. Chemical Society Reviews, 2016, 45(18): 5107-5134.
17	LI J, LIU R R, ZHU J Y, et al. Electrophoretic nuclei assembly of MOFs in polyamide membranes for enhanced nanofiltration[J]. Desalination, 2021, 512: 115-125.
18	ZHAO B, GUO Z Q, WANG H L, et al. Enhanced water permeance of a polyamide thin-film composite nanofiltration membrane with a metal-organic framework interlayer[J]. Journal of Membrane Science, 2021, 625: 119-154.
19	LI N, WANG Z, WANG M, et al. Swelling-controlled positioning of nanofillers through a polyamide layer in thin-film nanocomposite membranes for CO₂ separation[J]. Journal of Membrane Science, 2021, 624: 119095.
20	HOWARTH A J, LIU Y Y, LI P, et al. Chemical, thermal and mechanical stabilities of metal-organic frameworks[J]. Nature Reviews Materials, 2016, 1: 15018.
21	Ma X H, Yao Z, Yang Z, et al. Nanofoaming of polyamide desalination membranes to tune permeability and selectivity[J]. Environmental Science & Technology Letters, 2018, 5(2): 123-130.
22	BURTCH N C, JASUJA H, WALTON K S. Water stability and adsorption in metal-organic frameworks[J]. Chemical Reviews, 2014, 114(20): 10575-10612.
23	ZHANG X, WANG B, ALSALME A, et al. Design and applications of water-stable metal-organic frameworks: status and challenges[J]. Coordination Chemistry Reviews, 2020, 423: 213507.
24	ZHAO Y Y, LIU Y L, WANG X M, et al. Impacts of metal-organic frameworks on structure and performance of polyamide thin-film nanocomposite membranes[J]. ACS Applied Materials & Interfaces, 2019, 11(14): 13724-13734.
25	ECHAIDE-GÓRRIZ C, SORRIBAS S, TÉLLEZ C, et al. MOFs nanoparticles of MIL-68(Al), MIL-101(Cr) and ZIF-11 for thin film nanocomposite organic solvent nanofiltration membranes[J]. RSC Advances, 2016, 6(93): 90417-90426.
26	NAVARRO M, BENITO J, PASETA L, et al. Thin-film nanocomposite membrane with the minimum amount of MOFs by the Langmuir-Schaefer technique for nanofiltration[J]. ACS Applied Materials & Interfaces, 2018, 10(1): 1278-1287.
27	INGOLE P G, SOHAIL M, ABOU-ELANWAR A M, et al. Water vapor separation from flue gas using MOFs incorporated thin film nanocomposite hollow fiber membranes[J]. Chemical Engineering Journal, 2018, 334: 2450-2458.
28	HE M L, WANG L, LV Y, et al. Novel polydopamine/metal organic framework thin film nanocomposite forward osmosis membrane for salt rejection and heavy metal removal[J]. Chemical Engineering Journal, 2020, 389: 124452.
29	BONNETT B L, SMITH E D, DE LA GARZA M, et al. PCN-222 metal-organic framework nanoparticles with tunable pore size for nanocomposite reverse osmosis membranes[J]. ACS Applied Materials & Interfaces, 2020, 12(13): 15765-15773.
30	ECHAIDE-GÓRRIZ C, ZAPATA J A, ETXEBERRÍA-BENAVIDES M, et al. Polyamide/MOFs bilayered thin film composite hollow fiber membranes with tuned MOFs thickness for water nanofiltration[J]. Separation and Purification Technology, 2020, 236: 116265.
31	SARANGO L, PASETA L, NAVARRO M, et al. Controlled deposition of MOFs by dip-coating in thin film nanocomposite membranes for organic solvent nanofiltration[J]. Journal of Industrial and Engineering Chemistry, 2018, 59: 8-16.
32	XU Y, GAO X L, WANG X J, et al. Highly and stably water permeable thin film nanocomposite membranes doped with MIL-101 (Cr) nanoparticles for reverse osmosis application[J]. Materials, 2016, 9(11): 870.
33	LIU H R, GAO J, LIU G H, et al. Enhancing permeability of thin film nanocomposite membranes via covalent linking of polyamide with the incorporated metal-organic frameworks[J]. Industrial & Engineering Chemistry Research, 2019, 58(20): 8772-8783.
34	ALJUNDI I H. Desalination characteristics of TFN-RO membrane incorporated with ZIF-8 nanoparticles[J]. Desalination, 2017, 420: 12-20.
35	ABDULLAH N, YUSOF N, ISMAIL A F, et al. Insights into metal-organic frameworks-integrated membranes for desalination process: a review[J]. Desalination, 2021, 500: 114867.
36	LI X, LIU Y X, WANG J, et al. Metal-organic frameworks based membranes for liquid separation[J]. Chemical Society Reviews, 2017, 46(23): 7124-7144.
37	LIU H R, ZHANG M, ZHAO H, et al. Enhanced dispersibility of metal-organic frameworks (MOFs) in the organic phase via surface modification for TFN nanofiltration membrane preparation[J]. RSC Advances, 2020, 10(7): 4045-4057.
38	WEN Y, ZHANG X R, LI X S, et al. Metal-organic framework nanosheets for thin-film composite membranes with enhanced permeability and selectivity[J]. ACS Applied Nano Materials, 2020, 3(9): 9238-9248.
39	LEE T H, PARK I, OH J Y, et al. Facile preparation of polyamide thin-film nanocomposite membranes using spray-assisted nanofiller predeposition[J]. Industrial & Engineering Chemistry Research, 2019, 58(10): 4248-4256.
40	PEI J Y, SHAO K, ZHANG L, et al. Current status of microporous metal-organic frameworks for hydrocarbon separations[J]. Topics in Current Chemistry, 2019, 377(6): 1-34.
41	FURUKAWA H, CORDOVA K E, O’KEEFFE M, et al. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341(6149): 1230444.
42	DAI R B, WANG X Y, TANG C Y, et al. Dually charged MOFs-based thin-film nanocomposite nanofiltration membrane for enhanced removal of charged pharmaceutically active compounds[J]. Environmental Science & Technology, 2020, 54(12): 7619-7628.
43	XU T T, SHENG F M, WU B, et al. Ti-exchanged UiO-66-NH₂-containing polyamide membranes with remarkable cation permselectivity[J]. Journal of Membrane Science, 2020, 615: 118608.
44	WANG F H, ZHENG T, WANG P P, et al. Enhanced water permeability and antifouling property of coffee-ring-textured polyamide membranes by in situ incorporation of a zwitterionic metal-organic framework[J]. Environmental Science & Technology, 2021, 55(8): 5324-5334.
45	YANG Z, SUN P F, LI X H, et al. A critical review on thin-film nanocomposite membranes with interlayered structure: mechanisms, recent developments, and environmental applications[J]. Environmental Science & Technology, 2020, 54(24): 15563-15583.
46	KARAN S, JIANG Z W, LIVINGSTON A G. Sub-10nm polyamide nanofilms with ultrafast solvent transport for molecular separation[J]. Science, 2015, 348(6241): 1347-1351.
47	WU X N, YANG L, MENG F B, et al. ZIF-8-incorporated thin-film nanocomposite (TFN) nanofiltration membranes: importance of particle deposition methods on structure and performance[J]. Journal of Membrane Science, 2021, 632: 119356.
48	ZHU J Y, HOU J W, YUAN S S, et al. MOFs-positioned polyamide membranes with a fishnet-like structure for elevated nanofiltration performance[J]. Journal of Materials Chemistry A, 2019, 7(27): 16313-16322.
49	ZHU C Y, LI H N, YANG J, et al. Vacuum-assisted diamine monomer distribution for synthesizing polyamide composite membranes by interfacial polymerization[J]. Journal of Membrane Science, 2020, 616: 118557.
50	SORRIBAS S, GORGOJO P, TÉLLEZ C, et al. High flux thin film nanocomposite membranes based on metal-organic frameworks for organic solvent nanofiltration[J]. Journal of the American Chemical Society, 2013, 135(40): 15201-15208.
51	WANG L Y, FANG M Q, LIU J, et al. Layer-by-layer fabrication of high-performance polyamide/ZIF-8 nanocomposite membrane for nanofiltration applications[J]. ACS Applied Materials & Interfaces, 2015, 7(43): 24082-24093.
52	JI Y L, GU B X, XIE S J, et al. Superfast water transport zwitterionic polymeric nanofluidic membrane reinforced by metal-organic frameworks[J]. Advanced Materials, 2021, 33(38): 2102292.
53	ZHANG X, WAN K, SUBRAMANIAN P, et al. Electrochemical deposition of metal-organic framework films and their applications[J]. Journal of Materials Chemistry A, 2020, 8(16): 7569-7587.
54	VAN GOETHEM C, VERBEKE R, HERMANS S, et al. Controlled positioning of MOFs in interfacially polymerized thin-film nanocomposites[J]. Journal of Materials Chemistry A, 2016, 4(42): 16368-16376.
55	GHOSH A K, HOEK E M V. Impacts of support membrane structure and chemistry on polyamide-polysulfone interfacial composite membranes[J]. Journal of Membrane Science, 2009, 336(1/2): 140-148.
56	PARK H M, JEE K Y, LEE Y T. Preparation and characterization of a thin-film composite reverse osmosis membrane using a polysulfone membrane including metal-organic frameworks[J]. Journal of Membrane Science, 2017, 541: 510-518.
57	MA D C, PEH S B, HAN G, et al. Thin-film nanocomposite (TFN) membranes incorporated with super-hydrophilic metal-organic framework (MOFs) UiO-66: toward enhancement of water flux and salt rejection[J]. ACS Applied Materials & Interfaces, 2017, 9(8): 7523-7534.
58	ZIREHPOUR A, RAHIMPOUR A, ARABI SHAMSABADI A, et al. Mitigation of thin-film composite membrane biofouling via immobilizing nano-sized biocidal reservoirs in the membrane active layer[J]. Environmental Science & Technology, 2017, 51(10): 5511-5522.
59	席丹, 曹从军, 齐萨仁, 等. 超薄皮层反渗透复合膜制备技术的研究进展[J]. 化工进展, 2020, 39(10): 4073-4080.
	XI Dan, CAO Congjun, QI Saren, et al. Progress in preparation of ultra-thin composite reverse osmosis membrane[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4073-4080.
60	LIU L F, XIE X, QI S R, et al. Thin film nanocomposite reverse osmosis membrane incorporated with UiO-66 nanoparticles for enhanced boron removal[J]. Journal of Membrane Science, 2019, 580: 101-109.
61	杨丰瑞, 王志, 燕方正, 等. 纳滤用于一价/二价无机盐溶液分离研究进展[J]. 化工学报, 2021, 72(2): 799-813.
	YANG Fengrui, WANG Zhi, YAN Fangzheng, et al. Progress in separation of monovalent/divalent inorganic salt solutions by nanofiltration[J]. CIESC Journal, 2021, 72(2): 799-813.
62	卫旺, 相里粉娟, 金万勤, 等. 耐溶剂纳滤膜[J]. 化学进展, 2007, 19(10): 1592-1597.
	WEI Wang, XIANGLI Fenjuan, JIN Wanqin, et al. Solvent resistant nanofiltration membranes[J]. Progress in Chemistry, 2007, 19(10): 1592-1597.
63	GUO X Y, LIU D H, HAN T T, et al. Preparation of thin film nanocomposite membranes with surface modified MOFs for high flux organic solvent nanofiltration[J]. AIChE Journal, 2017, 63(4): 1303-1312.
64	CHENG X Q, JIANG X, ZHANG Y Q, et al. Building additional passageways in polyamide membranes with hydrostable metal organic frameworks to recycle and remove organic solutes from various solvents[J]. ACS Applied Materials & Interfaces, 2017, 9(44): 38877-38886.
65	YU S W, LI S C, HUANG S L, et al. Covalently bonded zeolitic imidazolate frameworks and polymers with enhanced compatibility in thin film nanocomposite membranes for gas separation[J]. Journal of Membrane Science, 2017, 540: 155-164.

[1]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[2]	潘宜昌, 周荣飞, 邢卫红. 高效分离同碳数烃的先进微孔膜：现状与挑战[J]. 化工进展, 2023, 42(8): 3926-3942.
[3]	常晓青, 彭东来, 李东洋, 张延武, 王景, 张亚涛. MOFs基丙烯/丙烷高效分离混合基质膜研究进展[J]. 化工进展, 2023, 42(4): 1961-1973.
[4]	张金辉, 张焕, 朱新锋, 宋忠贤, 康海彦, 刘红盼, 邓炜, 侯广超, 李桂亭, 黄真真. UiO-66复合材料用于典型有机污染物吸附和光催化氧化的研究进展[J]. 化工进展, 2023, 42(1): 445-456.
[5]	张彦, 汪伟, 谢锐, 巨晓洁, 刘壮, 褚良银. 负载酶@ZIF-8复合物的聚合物微颗粒可控制备[J]. 化工进展, 2022, 41(4): 2022-2028.
[6]	王志, 原野, 生梦龙, 李庆华. 膜法碳捕集技术——研究现状及展望[J]. 化工进展, 2022, 41(3): 1097-1101.
[7]	陈运涛, 董晓旭, 王洋, 王健男, 崔美, 黄仁亮. 巯基化Zr-MOFs/聚酯无纺布复合材料制备及应用[J]. 化工进展, 2022, 41(2): 854-861.
[8]	张新宇, 赵祯霞. 金属有机骨架基复合相变储热材料研究进展[J]. 化工进展, 2022, 41(12): 6408-6418.
[9]	高逸飞, 易群, 齐凯, 高丽丽, 李雪莲. MOFs基膜材料的研究现状及其在H₂/CH₄分离中的应用[J]. 化工进展, 2022, 41(12): 6395-6407.
[10]	孟子豪, 李青云, 刘幽燕, 林东亮, 唐爱星. 单相体系中MOF固定化脂肪酶催化柠檬烯环氧化[J]. 化工进展, 2022, 41(12): 6540-6548.
[11]	李航, 杨鸿辉, 石博方, 延卫. MOFs及其衍生物在非均相Fenton催化中应用的研究进展[J]. 化工进展, 2022, 41(11): 5811-5819.
[12]	张逸, 刘东昊, 丁一刚. 膜技术分离稀土金属元素的研究进展[J]. 化工进展, 2022, 41(10): 5567-5577.
[13]	马蕾, 张飞飞, 宋志强, 杨江峰, 李立博, 李晋平. 金属有机骨架材料用于吸附分离CH₄和N₂的研究进展[J]. 化工进展, 2021, 40(9): 5107-5117.
[14]	李志录, 王敏, 赵有璟, 彭正军, 白露. 膜特征对锂资源提取过程的影响[J]. 化工进展, 2021, 40(9): 5061-5072.
[15]	蒋博龙, 史顺杰, 蒋海林, 封鑫, 孙好芬. 金属有机框架材料吸附处理苯酚污水机理研究进展[J]. 化工进展, 2021, 40(8): 4525-4539.