Recent progress of MOF glasses based gas separation membrane

doi:10.11949/0438-1157.20241180

CIESC Journal ›› 2025, Vol. 76 ›› Issue (5): 2158-2168.DOI: 10.11949/0438-1157.20241180

• Reviews and monographs • Previous Articles Next Articles

Recent progress of MOF glasses based gas separation membrane

Zibo YANG¹(), Youfa WANG², Hansong YUE², Shuangjie YUAN³, Fujiang GENG¹(), Qingqing LI¹, De AO⁴, Bin LI¹, Mao YE⁴, Zhenjie GU⁴, Zhihua QIAO⁴()

^1.Hebei Key Laboratory of Heterocyclic Compounds, Hebei Center for New Inorganic Optoelectronic Nanomaterial Research, Technology Innovation Center of Nanosized Natural Products and New Materials of Hebei Province, Handan University, Handan 056005, Hebei, China
^2.Construction Project Management Branch, PipeChina Co. , Ltd. , Langfang 065000, Hebei, China
^3.China Petroleum Pipeline Engineering Corporation, Langfang 065000, Hebei, China
^4.State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China

Received:2024-10-24 Revised:2024-12-16 Online:2025-06-13 Published:2025-05-25
Contact: Fujiang GENG, Zhihua QIAO

MOF玻璃基气体分离膜的研究进展

杨紫博¹(), 王有发², 岳寒松², 远双杰³, 耿付江¹(), 李晴晴¹, 奥德⁴, 李斌¹, 叶茂⁴, 顾振杰⁴, 乔志华⁴()

^1.邯郸学院河北省杂环化合物重点实验室，河北省高校纳米无机光电新材料应用技术研发中心，河北省纳米化天然产物新材料技术创新中心，河北邯郸 056005
^2.国家管网集团项目管理分公司，河北廊坊 065000
^3.中国石油天然气管道工程有限公司，河北廊坊 065000
^4.天津工业大学省部共建分离膜与膜过程国家重点实验室，天津 300387

通讯作者: 耿付江,乔志华
作者简介:杨紫博（1991—），男，博士，教授，yangzibo0125@163.com
基金资助:
河北省教育厅科学研究项目(BJK2024029);邯郸市科技专项计划自筹经费项目(23422404147ZC);河北省重点研发项目(22373709D);国家自然科学基金项目(22408276);邯郸市科技研发投入引导计划项目(19422041001-9)

Abstract

Abstract:

In recent years, metal-organic frameworks (MOFs) glass materials obtained by melt-quenching of MOFs have attracted the attention of many researchers. After melt-quenching treatment, MOF crystals transform from long-range ordered crystal states to short-range ordered and long-range disordered amorphous glass states. During the transformation process, MOF glass effectively eliminates non-selective grain boundaries, ensuring the uniformity and consistency of the material. The excellent processability and formability of MOF glass enable it to be easily prepared into membrane materials of various shapes and sizes. The permanent and accessible pore structure of MOF glass gives it the ability to selectively adsorb different types of gases. For this reason, MOF glass is expected to become a candidate material for high-performance separation membranes, promoting the continuous development of related research and applications. This article reviews the melting mechanism, classification, and latest research progress of MOF glass membranes used for gas separation. In addition, this article also discusses the challenges faced in the membrane production process and proposes possible future research directions.

Key words: metal-organic frameworks, MOF glasses, melt-quenching, separation membrane

摘要：

近年来，由金属-有机框架（metal-organic frameworks， MOFs）材料熔融-淬火得到的MOF玻璃引起了众多研究学者的关注。经过熔融-淬火处理，MOF晶体由长程有序的晶态转变为短程有序、长程无序的非晶玻璃态。在这一转化过程中，MOF玻璃有效地消除了非选择性的晶界，确保了材料的均匀性和一致性。MOF玻璃优异的可加工性和成型性，使其能够方便地制备成各种形状和尺寸的膜材料。MOF玻璃永久且可进入的孔结构，赋予其选择性吸附不同类型气体的能力。基于此，MOF玻璃有望成为高性能分离膜的候选材料，推动相关研究和应用的不断发展。本文综述了用于气体分离的MOF玻璃膜的熔融机理、分类和最新研究进展。此外，还讨论了膜生产过程中面临的挑战，并提出了未来可能的研究方向。

关键词: 金属-有机框架, MOF玻璃, 熔融-淬火, 分离膜

CLC Number:

TQ 028

Zibo YANG, Youfa WANG, Hansong YUE, Shuangjie YUAN, Fujiang GENG, Qingqing LI, De AO, Bin LI, Mao YE, Zhenjie GU, Zhihua QIAO. Recent progress of MOF glasses based gas separation membrane[J]. CIESC Journal, 2025, 76(5): 2158-2168.

杨紫博, 王有发, 岳寒松, 远双杰, 耿付江, 李晴晴, 奥德, 李斌, 叶茂, 顾振杰, 乔志华. MOF玻璃基气体分离膜的研究进展[J]. 化工学报, 2025, 76(5): 2158-2168.

Figures/Tables 10

Fig.1 Schematic diagram of the formation process of MOF glass[29]

Fig.2 Schematic diagram of the transformation between MOF crystals and MOF glasses[52]

Fig.3 The development history of MOF glasses[24-25, 28-29, 39, 54-55]

Fig.4 (a) Preparation process of ZIF-62 glass membrane; (b) Gas separation performance and ideal selectivity of ZIF-62 glass membrane[60]

Fig.5 (a) Process diagram for preparing glass membrane by hot-pressing method; (b) Membrane separation performance[61]

Fig.6 (a) Schematic diagram of preparation process of ZIF-62 glass foam membrane; (b) Separation performance of ZIF-62 glass foam membrane and (c) performance comparison[62]

Fig.7 Tomography and thermal analysis curves of blended MOF glass[63]

Fig.8 ag[ZIF-62/ZIF-8] mixed matrix membrane: (a) preparation process; (b) dynamic adsorption test; (c) transport model of C2H6 molecule across the membrane; (d) mixed gas C2H6 permeance and C2H6/C2H4 selectivity; (e) pure gas C2H6 permeance and C2H6/C2H4 selectivity[65]

Fig.9 MIL-53/ZIF-62 glass composite material: (a) formation process of composite material; (b) schematic diagram of ZIF-62 glass fixing effect on MIL-53 crystal aperture; (c) X-ray diffraction pattern of MIL-53/ZIF-62 glass composite material; (d) CO2 adsorption isotherms of MIL-53/ZIF-62 glass composite material[66-67]

Table 1 Classification of MOF glass based gas separation membranes

类别	膜名称	分离体系	通量	选择性	文献
纯MOF玻璃膜	a_gfZIF-62	CH₄/N₂	37000 GPU	5.12	[62]
	a_gTIF-4	CO₂/N₂	3×10^-9mol/(m²·s·Pa)	27	[75]
	a_gZIF-62	H₂/CH₄	70 GPU	59	[76]
共混MOF玻璃膜	a_g[ZIF-62/ZIF-8]	C₂H₆/C₂H₄	41569 GPU	7.16	[65]
共混MOF玻璃膜	a_g[ZIF-62/ZIF-7]	H₂/CH₄	120.3 GPU	98.6	[77]
晶体-MOF玻璃膜	(a_gZIF-62)_1-_x (4A) _x	CO₂/CH₄	33.3 GPU	31.7	[78]
	(a_gZIF-62)_1-_x (SSZ-13) _x (a_gZIF-62)_1-_x (SSZ-13) _x	1,3-C₄H₆/i-C₄H₁₀ 1,3-C₄H₆/i-C₄H₁₀	693.00 GPU 537.37 GPU	11.94 8.98	[73]
	MIL-101/a_gZn-P-dmbIm	CO₂/N₂	68.5 GPU	61	[74]

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Recent progress of MOF glasses based gas separation membrane

MOF玻璃基气体分离膜的研究进展

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