Progress in water stable and water absorption applications of metal-organic frameworks

doi:10.16085/j.issn.1000-6613.2021-2040

Abstract

Abstract:

Water vapor is widely present in air and industrial gases and its collection and removal requires the use of adsorbents with high water absorption and storage capacity. Metal-organic frameworks (MOFs), as a new type of porous material with high porosity and high specific surface area, have the characteristics of both mesh structure and controlled pore size adjustment, and are widely studied in various fields such as adsorption, separation, catalysis and filtration. The application of MOFs in water adsorption requires not only high-water stability, but also hydrophilic and adsorption-desorption cycle capabilities. This paper reviewed the basic composition of water-stable MOFs, the design principles based on Pearson’s soft and hard acid-base theory, the factors influencing the water adsorption behavior and the progress of applications such as air water harvesting and gas dehumidification. The physical parameters of 13 water adsorption MOFs and their derivatives with reference to the saturation moisture absorption were listed. Finally, the problems in the synthesis mechanism, batch preparation and application of water adsorption MOFs were summarized, and the corresponding solutions were proposed, which were expected to provide valuable references for the research direction of MOFs in water adsorption applications.

Key words: metal-organic framework materials, porous absorbent materials, water stability, water adsorption mechanism

摘要：

水蒸气广泛存在于空气和工业气体中，收集利用或去除水蒸气都需要利用高吸水储水的吸附剂。金属有机框架材料（metal-organic frameworks，MOFs）作为一种具有高孔隙率、高比表面积的新型多孔材料，同时具备网状结构和孔径可控调节的特性，被广泛应用于吸附、分离、催化、过滤等多个领域。将MOFs应用于水吸附领域不仅要求MOFs具备较高的水稳定性，还需要具备亲水和吸附-脱附循环能力。本文综述了水稳定性MOFs的基本组成，基于皮尔森软硬酸碱理论的设计原则，水吸附行为的影响因素以及空气集水、气体除湿等应用领域的进展，以饱和吸湿量为参考罗列了13种水吸附MOFs及其衍生物的物理参数。最后总结了水吸附MOFs在合成机理、批量制备和应用领域存在的问题，并对应提出了解决思路，期望为MOFs在水吸附应用的研究方向提供有价值的参考。

关键词: 金属有机框架材料, 多孔吸水材料, 水稳定性, 水吸附机制

CLC Number:

O611

ZU Mei, XU Haitao, XIE Wei, CHENG Haifeng. Progress in water stable and water absorption applications of metal-organic frameworks[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4254-4267.

祖梅, 许海涛, 谢炜, 程海峰. 金属有机框架材料的水稳定性及吸水应用进展[J]. 化工进展, 2022, 41(8): 4254-4267.

Figures/Tables 17

References 103

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MOFs名称	饱和吸附量/g?g^-1	孔径/?	配体	参考文献
NU-1500-Cr	1.02	14	Triptycene	[83]
NU-1500-Fe	—	14	Triptycene	[83]
NU-1500-Sc	—	14	Triptycene	[83]
Cr-soc-MOF-1	1.95	—	H₄TCPT	[84]
MIL-101(Cr)	1.40	29,34	BDC	[72, 85]
MIL-101(Cr)-NH₂	1.05	—	BDC-NH₂	[86]
MIL-101(Cr)-NO₂	0.45	—	BDC-NO₂	[86]
MIL-101(Cr)-SO3H	0.95	—	BDC-SO3H	[87]
UiO-66(Zr)	0.36	7.4,8.4	BDC	[72]
UiO-66(Zr)-NH₂	0.36	—	BDC-NH₂	[72]
(Mg)MOF-74	0.63	11.1	DOT	[88]
(Ni)MOF-74	0.51	—	DOT	[89]
(Co)MOF-74	0.49	—	DOT	[89]
Ni-MOF-74-BPP	0.81	17	BPP	[90]
Ni-MOF-74-TPP	0.9	23	TPP	[90]
HV-MOF-1	0.59	—	H₂dcbp	[91]
LiCl@MIL-101(Cr)	0.77	—	BDC	[92]
(Al)MOF-303	1.30	—	Fumarate	[79]
Ni₂Cl₂BTDD	1.07	38	H₂BTDD	[93]
Ni₂Br₂BTDD	0.76	38	H₂BTDD	[93]
Zr-MOF-808	0.74	18.4	BTC	[94]
Zr-MOF-801	0.46	4.8,7.4	Fumarate	[64]
BIT-66	0.55	65	H₃BTB	[95]
Y-shp-MOF-5	0.45	12	BTEB	[96]

MOFs名称	饱和吸附量/g?g^-1	孔径/?	配体	参考文献
NU-1500-Cr	1.02	14	Triptycene	[83]
NU-1500-Fe	—	14	Triptycene	[83]
NU-1500-Sc	—	14	Triptycene	[83]
Cr-soc-MOF-1	1.95	—	H₄TCPT	[84]
MIL-101(Cr)	1.40	29,34	BDC	[72, 85]
MIL-101(Cr)-NH₂	1.05	—	BDC-NH₂	[86]
MIL-101(Cr)-NO₂	0.45	—	BDC-NO₂	[86]
MIL-101(Cr)-SO3H	0.95	—	BDC-SO3H	[87]
UiO-66(Zr)	0.36	7.4,8.4	BDC	[72]
UiO-66(Zr)-NH₂	0.36	—	BDC-NH₂	[72]
(Mg)MOF-74	0.63	11.1	DOT	[88]
(Ni)MOF-74	0.51	—	DOT	[89]
(Co)MOF-74	0.49	—	DOT	[89]
Ni-MOF-74-BPP	0.81	17	BPP	[90]
Ni-MOF-74-TPP	0.9	23	TPP	[90]
HV-MOF-1	0.59	—	H₂dcbp	[91]
LiCl@MIL-101(Cr)	0.77	—	BDC	[92]
(Al)MOF-303	1.30	—	Fumarate	[79]
Ni₂Cl₂BTDD	1.07	38	H₂BTDD	[93]
Ni₂Br₂BTDD	0.76	38	H₂BTDD	[93]
Zr-MOF-808	0.74	18.4	BTC	[94]
Zr-MOF-801	0.46	4.8,7.4	Fumarate	[64]
BIT-66	0.55	65	H₃BTB	[95]
Y-shp-MOF-5	0.45	12	BTEB	[96]