金属有机骨架膜的制备与应用进展

doi:10.16085/j.issn.1000-6613.2018-1094

化工进展 ›› 2019, Vol. 38 ›› Issue (01): 467-484.DOI: 10.16085/j.issn.1000-6613.2018-1094

金属有机骨架膜的制备与应用进展

周胜(),侯倩倩,魏嫣莹(),王海辉()

华南理工大学化学与化工学院，广东广州 510640

收稿日期:2018-05-28 修回日期:2018-09-17 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 魏嫣莹,王海辉
作者简介:周胜（1994—），男，硕士研究生，研究方向为金属有机骨架膜。E-mail：<email>zhou.sheng@mail.scut.edu.cn</email>。|魏嫣莹，研究员，硕士生导师，研究方向为膜分离技术。E-mail：<email>ceyywei@scut.edu.cn</email>|王海辉，教授，博士生导师，研究方向为无机膜。E-mail:<email>hhwang@scut.edu.cn</email>
基金资助:
国家自然科学基金(21536005，51621001，21606086);广东省自然科学基金(2014A030312007，2017A030306002);广州市科技项目(201707010317);国家自然科学基金（21536005，51621001，21606086）；广东省自然科学基金（2014A030312007，2017A030306002）；广州市科技项目（201707010317）。

Recent progress on the preparation and applications of metal organic framework membranes

Sheng ZHOU(),Qianqian HOU,Yanying WEI(),Haihui WANG()

School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China

Received:2018-05-28 Revised:2018-09-17 Online:2019-01-05 Published:2019-01-05
Contact: Yanying WEI,Haihui WANG

摘要/Abstract

摘要：

膜分离技术因其高效节能的特点，被认为是最有前景的分离技术之一。由于众多待分离的混合组分在物理性质（如尺寸）上极为接近，实现精确的膜分离仍具有极大的挑战。金属有机骨架材料具有孔径精确可调、孔隙率高等优点，使其有望实现对尺寸相近分子的精确筛分，因此可以作为理想的膜材料。本文对传统的多孔膜材料进行了比较，并对基于金属有机骨架材料的多孔膜进行了分类，包括支撑型金属有机骨架膜和混合基质膜。同时，系统地总结了两大类金属有机骨架膜的制备方法及其发展历程，对先进的膜制备技术进行了展望；总结了金属有机骨架膜在气体分离、纳滤及海水淡化、渗透汽化等方面的应用。最后，针对支撑型金属有机骨架膜提出了改善其透量和选择性的思路。

关键词: 膜, 分离, 分子筛, 气体, 渗透

Abstract:

Membrane-based separation is considered to be one of the most promising separation technologies due to its high efficiency and low energy consumption. Owing to the small difference in the mixtures’ physical properties (such as molecular sizes), it is extremely challenging to finely separate them. Metal-organic frameworks are featured to have good adjustability on aperture sizes and high porosity, thus are expected as ideal membrane materials to sieve molecules precisely. In this review, traditional porous membrane materials are compared and the metal-organic framework based membranes are classified into supported metal-organic framework membranes and mixed matrix membranes. Simultaneously, the fabrication methods and their developments of these two types of membranes are introduced and the more advanced fabrication methods are forecasted. Additionally, the applications of metal-organic framework membranes in gas separation, nanofiltration and desalination, and pervaporation are discussed. Finally, several directions to improve the permeability and selectivity of supported metal-organic framework membranes are proposed.

Key words: membrane, separation, molecular sieves, gas, permeation

中图分类号:

TB383

周胜, 侯倩倩, 魏嫣莹, 王海辉. 金属有机骨架膜的制备与应用进展[J]. 化工进展, 2019, 38(01): 467-484.

Sheng ZHOU, Qianqian HOU, Yanying WEI, Haihui WANG. Recent progress on the preparation and applications of metal organic framework membranes[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 467-484.

图/表 21

图1 膜分离的模型示意图

图2 分子尺寸差异为0.5～0.4?、 0.4～0.25?和0.25～0.1?的混合物的分离难度分类[2]

图3 PIM-1分子模型图和PIM-1膜的照片[10]

图4 MIL-53材料的呼吸效应示意图

图5 沸石分子筛、MOFs和PIMs在稳定孔隙率、结构多样性、化学可调性、加工性能方面的比较

图6 溶剂热法制备纯MOF膜过程示意图

图7 APTES修饰多孔基底用于ZIF-90膜的示意图[29]

图8 LDH修饰的基底用于生长ZIF-8膜的示意图[32]

图9 电沉积引入无机修饰物制备MOF膜示意图[33]

图10 LBL法制备MOF膜示意图[40]

图11 旋涂法制备ZIF-8膜示意图[46]

图12 MMM的制备流程[15]

图13 PSP制备MMM的原理及其过程示意图[60]（图片版权来源于John Wiley and Sons）

图14 PSP制备的膜与普通MMM和纯MOF膜的比较[15]

图15 抗H2S气体的MMM示意图[72]

图16 膜孔大于水合离子时和ZIF-8膜用于离子筛分过程示意图[75]

图17 渗透汽化过程示意图[15]

图18 超薄的Zn2(bim)4纳米片[86]

图19 分子在定向孔道和随机孔道传输路线比较

图20 自牺牲模板法与原位晶种耦合的制备定向MOF膜的方法示意图[88]

图21 双配体MOFs示意图[95]

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金属有机骨架膜的制备与应用进展

Recent progress on the preparation and applications of metal organic framework membranes

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