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化学进展 2023, Vol. 35 Issue (8): 1154-1167 DOI: 10.7536/PC230111 前一篇   后一篇

• 综述 •

MOF-聚合物混合基质膜的制备、改性及其在渗透汽化中的应用

张浩1, 伍艳辉1,2,*()   

  1. 1 同济大学化学科学与工程学院 上海 200092
    2 同济大学上海市化学品分析、风险评估与控制重点实验室 上海 200092
  • 收稿日期:2023-01-30 修回日期:2023-03-12 出版日期:2023-08-24 发布日期:2023-04-20
  • 作者简介:

    伍艳辉 博士,教授,博士生导师,分别于1994年和1999年毕业于天津大学化工系/化工学院,获学士学位和博士学位;1999年进入同济大学化学系/化学科学与工程学院工作,2010年到美国加州大学伯克利分校做访问学者。研究方向:渗透汽化、正渗透、纳滤等膜过程和膜材料的研究。

  • 基金资助:
    国家重点研发计划项目(2019YFC0408200); 国家自然科学基金项目(22078249)
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Preparation and Modification of MOF-Polymer Mixed Matrix Membrane and its Application in Pervaporation

Hao Zhang1, Yanhui Wu1,2()   

  1. 1 School of Chemical Science and Engineering, Tongji University,Shanghai 200092, China
    2 Shanghai Key Laboratory of Chemical Assessment and Sustainability, Tongji University, Shanghai 200092, China
  • Received:2023-01-30 Revised:2023-03-12 Online:2023-08-24 Published:2023-04-20
  • Contact: *email:wuyanhui@tongji.edu.cn
  • Supported by:
    National Key Research and Development Program of China(2019YFC0408200); National Natural Science Foundation of China(22078249)

渗透汽化是一种具有能耗低、操作简便等优点的膜分离技术,目前传统聚合物渗透汽化膜在分离性能和稳定性等方面还有欠缺。金属有机框架(MOF)是由金属离子与有机配体以自组装形式组建而成的晶态多孔材料,具有独特的性质,如对目标分子的选择性吸附和分子筛分效应,近年来许多研究表明将MOF作为填料引入聚合物基质中构筑混合基质膜(MMMs)对其渗透汽化性能有很好的促进作用。本文从MOF的不同系列出发,讨论了适用于渗透汽化混合基质膜的MOF种类,分析了MOF-聚合物混合基质膜的制备方法与改性策略,综述了该类混合基质膜在渗透汽化方面(有机溶剂脱水、从稀溶液中回收有机物、有机混合物的分离)的应用进展,总结了用于渗透汽化的MOF-聚合物混合基质膜研究面临的挑战,并对其未来发展提出展望。

关键词： 渗透汽化, 金属有机框架, 混合基质膜, 改性

Pervaporation is a membrane separation technology with the advantages of low energy consumption and easy operation. At present, the traditional polymer pervaporation membrane still lacks in separation performance and stability. Metal-organic framework (MOF) is a crystalline porous material formed by self-assembly of metal ions and organic ligands. It has unique properties such as selective adsorption of target molecules and molecular sieving effect. In recent years, many studies have shown that the introduction of MOF as a filler into the polymer matrix to construct mixed matrix membranes (MMMs) has a good effect on its pervaporation performance. Starting from different series of MOF, this paper discusses the types of MOF suitable for pervaporation mixed matrix membrane, analyzes the preparation methods and modification strategies of MOF-polymer mixed matrix membrane, and reviews the application progress of this kind of mixed matrix membrane in pervaporation (dehydration of organic solvent, recovery of organic matter from dilute solution, separation of organic mixture). The challenges in the research of MOF-polymer mixed matrix membrane for pervaporation are summarized, and its future development is prospected.

Contents

1 Introduction

2 Different series of MOFs for pervaporation

2.1 Introduction of different series of MOFs

2.2 Selection of MOF fillers

3 Preparation and modification strategies of MOF based MMMs

3.1 Preparation methods of MOF based MMMs

3.2 Modification strategies of MOF based MMMs

4 Application of MOF based MMMs in pervaporation

4.1 Solvent dehydration

4.2 Recovery of organic compounds from diluted aqueous solutions

4.3 Organic-organic mixture separation

5 Conclusion and outlook

Key words: pervaporation, metal-organic framework, mixed matrix membrane, modification
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图1 渗透汽化的原理
Fig.1 The principle of pervaporation
图2 不同类型MOF的结构图
Fig.2 Structure diagram of different types of MOFs
表1 IRMOF系列的主要特征
Table 1 Main features of IRMOF series
IRMOF series Center atom Pore size
(Å)		 Hydrophilicity/
hydrophobicity		 ref
IRMOF-1 Zn 15 Hydrophilicity 23
IRMOF-3 Zn 15 Hydrophilicity 24
IRMOF-14 Zn 20 Hydrophilicity 25
IRMOF-16 Zn 25 Hydrophilicity 25
表2 ZIF系列的主要特征
Table 2 Main features of ZIF series
ZIF series Center atom Pore size
(Å)		 Hydrophilicity/
hydrophobicity		 ref
ZIF-7 Zn 3.0 hydrophobicity 31
ZIF-8 Zn 3.4 hydrophobicity 32
ZIF-90 Zn 3.5 hydrophilicity 33
ZIF-71 Zn 13 hydrophobicity 34
ZIF-68 Zn 7.5 hydrophobicity 35
ZIF-67 Co 3.4 hydrophobicity 36
表3 MIL系列的主要特征
Table 3 Main features of MIL series
MIL series Center atom Pore size
(Å)		 Hydrophilicity/
hydrophobicity		 ref
MIL-53 Al 8.6 hydrophobicity 42
MIL-68 Al 6 Modifiable 43
MIL-88 Fe 12 Modifiable 44
MIL-100 Cr 25 hydrophobicity 45
MIL-100 Fe 25 Modifiable 46
MIL-101 Fe 23 Modifiable 47
MIL-101 Cr 29 Modifiable 48
表4 PCN系列的主要特征
Table 4 Main features of PCN series
PCN series Center atom Pore size
(Å)		 Hydrophilicity/
hydrophobicity		 ref
PCN-222 Zr 13 hydrophobicity 52
PCN-250 Fe 9.6 hydrophobicity 53
PCN-333 Al 11 hydrophobicity 54
PCN-777 Zr 38 hydrophobicity 55
PCN-222 Fe 13 hydrophobicity 56
表5 UiO系列的主要特征
Table 5 Main features of UiO series
UiO series Center atom Pore size (Å) Hydrophilicity/
hydrophobicity		 ref
UiO-66 Zr 6 hydrophilicity 60
UiO-68 Zr 17.7 Modifiable 61
UiO-67 Zr 11 Modifiable 62
NH2-UiO-66 Zr 8 Modifiable 63
UiO-66-SO3H Zr 8 Modifiable 64
UiO-66-(OH)2 Zr 7 Modifiable 65
图3 ILs修饰MIL-101制备MMMs[94]
Fig.3 Preparation of MMMs by ILs modified MIL-101[94]. Copyright 2021, J. Membr. Sci.
图4 ZIF-L基MMMs用于渗透汽化[118]
Fig.4 ZIF-L based MMMs for pervaporation[118]. Copyright 2019, J. Membr. Sci.
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