MOFs玻璃膜在气体分离领域的研究进展

doi:10.11949/0438-1157.20241230

摘要/Abstract

摘要：

金属有机框架（metal organic frameworks，MOFs）玻璃材料的出现与传统的MOFs材料形成了良好互补，凭借其独特的熔融特性及短程有序、长程无序的超微孔结构，有效避免了多晶MOFs膜存在的晶间缺陷以及MOFs基杂化膜中相界面不兼容问题，为气体分离膜领域带来了新的技术选择。首先回顾了MOFs玻璃材料的研究历程，系统总结了MOFs玻璃的制备方法，介绍了MOFs玻璃膜在气体分离领域的最新研究进展，最后针对MOFs玻璃膜气体分离发展面临的问题进行了分析，并提出了潜在的研究方向和解决方案。

关键词: MOFs玻璃, 复合膜, 气体分离, 孔隙调控, 合成, 传递

Abstract:

The advent of metal-organic frameworks (MOFs) glass materials serves to complement traditional MOFs materials effectively. With its unique melting characteristics and short-range ordered and long-range disordered ultra-microporous structure, it effectively avoids the intercrystalline defects in polycrystalline MOFs membranes and the incompatibility of phase interfaces in MOFs-based hybrid membranes, bringing new technical options to the field of gas separation membranes. The research history of MOFs glass materials is first reviewed, followed by a systematic summary of the preparation methods for MOFs glass. The latest advancements in the application of MOFs glass membranes in the field of gas separation are introduced. Finally, an analysis is conducted on the challenges faced by MOFs glass membranes in gas separation applications, and potential research directions and solutions are proposed.

Key words: MOFs glass, composite membrane, gas separation, pore regulation, synthesis, transport

中图分类号:

TQ 028.8

赵浩帆, 任豪杰, 刘宗凯, 董冠英, 张亚涛. MOFs玻璃膜在气体分离领域的研究进展[J]. 化工学报, 2025, 76(5): 2042-2054.

Haofan ZHAO, Haojie REN, Zongkai LIU, Guanying DONG, Yatao ZHANG. Research progress of MOFs glass membranes in gas separation applications[J]. CIESC Journal, 2025, 76(5): 2042-2054.

图/表 8

图1 （a）MOFs玻璃熔融-淬火过程[13]；（b）典型的ZIFs玻璃前体的晶体结构及对应熔化温度Tm和分解温度Td

Fig.1 (a) Melting-quenching process of MOFs glass[13]; (b) Crystal structures of typical ZIFs glass precursors and corresponding melting temperature Tm and decomposition temperature Td

图2 溶剂热、超声、机械球磨、电化学辅助合成方法示意图

Fig.2 Schematic representation of solvothermal， ultrasonic， mechanical ball milling and electrochemical assisted synthesis methods

图3 不同方法合成的ZIF-62的SEM图

Fig.3 SEM images of ZIF-62 prepared by different methods

图4 （a）ZIF-8配体交换过程示意图[52]；（b）UiO-67配体结构改造示意图[53]

Fig. 4 (a) Schematic diagram of the ligand exchange process of ZIF-8[52]; (b) Schematic diagram of the ligand structure modification of UiO-67[53]

图5 （a）ZIF-62玻璃膜的EDXS谱图[63]；（b）单气体渗透通量与气体分子动力学直径的函数关系[63]；（c）原子层沉积法制备的agZIF-62玻璃薄膜断面SEM图像[65]；（d）电化学辅助法制备的相应ZIF-62玻璃薄膜的断面SEM图像[51]；电化学辅助法制备玻璃膜的CO2/N2（e）和CO2/CH4（f）分离性能[51]

Fig.5 (a) EDXS patterns of ZIF-62 glass films[63]; (b) Single gas permeance as a function of gas kinetic diameter[63]; (c) SEM image of the cross-section of agZIF-62 glass films prepared by atomic layer deposition[65]; (d) SEM image of the cross-section of the corresponding ZIF-62 glass films prepared by electrochemical assisted method[51]; (e) CO2/N2 and (f) CO2/CH4 separation performance of electrochemically assisted method of preparation of glass films [51]

图6 （a）PEI分解过程对agfZIF-62形成的影响[69]；（b）agfZIF-62的高分辨率TEM图像[69]；（c）agfZIF-62膜的气体分离性能对比[69]

Fig.6 (a) Effect of PEI decomposition process on the formation of agfZIF-62[69]; (b) High-resolution TEM image of agfZIF-62[69]; (c) Comparison of gas separation performance of agfZIF-62 membrane[69]

图7 （a）CGC膜的制备工艺[75]；（b）C2H6分子跨膜运输模型[75]；（c）ag[(ZIF-62)1-X (ZIF-8) X ]膜气体分离性能[75]

Fig. 7 (a) Preparation process of CGC membranes[75]; (b) Modelling of transmembrane transport of C2H6 molecules[75]; (c) Gas separation properties of ag[(ZIF-62)1-X (ZIF-8) X ] membranes[75]

图8 （a）ZIF-62/PIM-1[(1)、(3)]与agZIF-62/PIM-1[(2)、(4)]断面SEM图[44]；（b）agZIF-62/PIM-1性能对比[44]；（c）ZIF-62/PBI[(1)、(3)]与agZIF-62/PBI[(2)、(4)]断面SEM图[80]；（d）agZIF-62/PBI性能对比[80]

Fig. 8 (a) Cross-sectional SEM images of ZIF-62/PIM-1 [(1), (3)] and agZIF-62/PIM-1 [(2), (4)][44]; (b) Comparison of agZIF-62/PIM-1 performance[44]; (c) Cross-sectional SEM images of ZIF-62/PBI [(1), (3)] and agZIF-62/PBI [(2), (4)][80]; (d) Comparison of agZIF-62/PBI performance[80]

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