Structural modulation and gas separation performance of Ni-MOF-74 metal-organic framework membranes

doi:10.11949/0438-1157.20241522

Abstract

Abstract:

Ni-MOF-74 metal-organic framework membranes were successfully prepared by solvothermal synthesis with nickel acetate and 2,5-dihydroxyterephthalic acid (DHTA) as raw materials. The influence of the ratio of nickel ions to DHTA on the crystal phase structure, micromorphology, and separation performance of the membrane material was systematically investigated. The Ni-MOF-74 membrane was fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG) and gas permeation test. The experiments show that the raw material ratio can significantly affect the crystal phase structure and micromorphology of Ni-MOF-74 membrane. As the ratio of nickel ions to the ligand increases, the grain size of the membrane gradually decreases, and the crystallinity of the membrane layer first increases and then decreases. When the molar ratio of metal ions to DHTA is 4∶1, the prepared Ni-MOF-74 membrane has the fewest defects. The results of the gas permeation separation test indicated that the ideal selectivity of H₂/CO₂ of this membrane exceeds 20, surpassing the Knudsen diffusion selectivity, demonstrating good H₂/CO₂ sieving ability.

Key words: membrane, separation, crystallization, raw material ratio, Ni-MOF-74, solvothermal synthesis

摘要：

以乙酸镍和 $2,5 -$ 二羟基对苯二甲酸（DHTA）为原料，通过溶剂热合成法成功制备了Ni-MOF-74金属有机框架膜，系统研究了镍离子与DHTA比例对膜晶相结构、微观形貌及分离性能的影响。利用X射线衍射（XRD）、扫描电镜（SEM）、热重（TG）和气体渗透测试等技术对Ni-MOF-74膜进行了全面表征。实验表明，原料配比会显著影响Ni-MOF-74膜的晶相结构与微观形貌，随着镍离子与配体比例的升高，膜片晶粒尺寸逐渐减小，膜层结晶度呈现先升后降的趋势。当金属离子与DHTA摩尔比为4∶1时，所制备的Ni-MOF-74膜缺陷最少。气体渗透分离测试结果显示，该膜H₂/CO₂理想选择性超20，超过其努森扩散选择性，展现出较好的H₂/CO₂筛分能力。

关键词: 膜, 分离, 结晶, 原料配比, Ni-MOF-74, 溶剂热合成法

CLC Number:

TQ 028.8

Bilin LIANG, Qian YU, Siqi JIA, Fang LI, Qiming LI. Structural modulation and gas separation performance of Ni-MOF-74 metal-organic framework membranes[J]. CIESC Journal, 2025, 76(6): 2714-2721.

梁碧麟, 余倩, 贾思琦, 李芳, 李其明. Ni-MOF-74金属有机框架膜的结构调变及气体分离性能研究[J]. 化工学报, 2025, 76(6): 2714-2721.

Figures/Tables 9

Fig.1 Schematic diagram of our measurement device for gas separation

Fig.2 Influence of the ratio of metal ions to ligands on the crystal structure of Ni-MOF-74 membrane

Fig.3 Effects of the ratio of metal ions to ligands on the evolution of the morphological structure of Ni-MOF-74 membrane

Fig.4 N2 adsorption-desorption isotherms of Ni-MOF-74 powders (the inserted picture is the pore size distribution diagram)

Fig.5 DTG-TGA curve of Ni-MOF-74 powders

Table 1 Single gas permeances and their ideal selectivity of the Ni-MOF-74 membranes

Ratio	Gas	Permeance/(10^-7 mol·m^-2·s^-1·Pa^-1)	H₂ ideal selectivity
1∶1	H₂	80.31
	N₂	25.23	3.18
	CO₂	21.15	3.84
2∶1	H₂	11.96
	N₂	5.45	2.20
	CO₂	2.93	4.09
3∶1	H₂	5.43
	N₂	2.41	2.25
	CO₂	1.25	4.34
4∶1	H₂	3.73
	N₂	1.06	3.53
	CO₂	0.18	20.63
5∶1	H₂	3.97
	N₂	1.44	2.77
	CO₂	0.67	5.93

Fig.6 Comparison of CO2 permeability of different Ni-MOF-74 membranes

Fig.7 Relationship between the permeance and the diameter of permeating molecules for Ni-MOF-74 membrane (4∶1)(the illustration shows the comparison of ideal selectivity and separation factor)

Table 2 Comparison of separation performance of different MOF separation membranes

Membrane samples	$Q H 2$ / (10^-8 mol·m^-2·s^-1·Pa^-1)	$Q C O 2$ / (10^-8 mol·m^-2·s^-1·Pa^-1)	Selectivity H₂/CO₂	Ref.
MOF-74	1270	140	9.1	[23]
ZIF-7	4.56	0.33	13.8	[24]
ZIF-8	2660	302.00	8.8	[25]
NH₂-MIL-53	538.95	60.67	8.9	[26]
UiO-66-NH₂	1.42	0.19	7.4	[27]
ZIF-8	0.38	0.04	10.5	[28]
CAU-10-H	19.03	10.62	1.8	[29]
ZIF-90	0.82	0.12	6.6	[30]
MIL-96(Al)	53	6.09	8.7	[31]
ZIF-67	148	8.81	16.8	[32]
Ni-MOF-74	37.3	1.8	20.63	this work

Table 2 Comparison of separation performance of different MOF separation membranes

Membrane samples	$Q H 2$ / (10^-8 mol·m^-2·s^-1·Pa^-1)	$Q C O 2$ / (10^-8 mol·m^-2·s^-1·Pa^-1)	Selectivity H₂/CO₂	Ref.
MOF-74	1270	140	9.1	[23]
ZIF-7	4.56	0.33	13.8	[24]
ZIF-8	2660	302.00	8.8	[25]
NH₂-MIL-53	538.95	60.67	8.9	[26]
UiO-66-NH₂	1.42	0.19	7.4	[27]
ZIF-8	0.38	0.04	10.5	[28]
CAU-10-H	19.03	10.62	1.8	[29]
ZIF-90	0.82	0.12	6.6	[30]
MIL-96(Al)	53	6.09	8.7	[31]
ZIF-67	148	8.81	16.8	[32]
Ni-MOF-74	37.3	1.8	20.63	this work

References 32

[1]	Yuan J P, Liu X Y, Wang H, et al. Evaluation and screening of porous materials containing fluorine for carbon dioxide capture and separation[J]. Computational Materials Science, 2023, 216: 111872.
[2]	乔智威, 杨仁党, 王海辉, 等. 面向生物甲烷分离的不同金属配位金属-有机骨架材料的分子设计[J]. 化工学报, 2014, 65(5): 1729-1735.
	Qiao Z W, Yang R D, Wang H H, et al. Molecular design of metal-organic frameworks with different metal ligands for bio-methane separation[J]. CIESC Journal, 2014, 65(5): 1729-1735.
[3]	曲云鹏, 张丙兴, 石金彪, 等. 钛基金属-有机框架材料的改性及其催化性能研究[J]. 化工学报, 2020, 71(1): 283-289.
	Qu Y P, Zhang B X, Shi J B, et al. Study on modification of titanium-based metal-organic framework and catalytic performance[J]. CIESC Journal, 2020, 71(1): 283-289, 430.
[4]	Sahayaraj A F, Prabu H J, Maniraj J, et al. Metal-organic frameworks (MOFs): the next generation of materials for catalysis, gas storage, and separation[J]. Journal of Inorganic and Organometallic Polymers and Materials, 2023, 33(7): 1757-1781
[5]	Jia T, Gu Y F, Li F T. Progress and potential of metal-organic frameworks (MOFs) for gas storage and separation: a review[J]. Journal of Environmental Chemical Engineering, 2022, 10(5): 108300.
[6]	林叶, 祝钰灵, 李伟华, 等. MOFs材料的CH₄存储研究进展[J]. 山东化工, 2021, 50(4): 82-84.
	Lin Y, Zhu Y L, Li W H, et al. Research progress of CH₄ storage in MOF materials[J]. Shandong Chemical Industry, 2021, 50(4): 82-84.
[7]	Xiao H, Low Z X, Gore D B, et al. Porous metal-organic framework-based filters: synthesis methods and applications for environmental remediation[J]. Chemical Engineering Journal, 2022, 430: 133160.
[8]	Wang J W, Fan S C, Li H P, et al. De-linker-enabled exceptional volumetric acetylene storage capacity and benchmark C₂H₂/C₂H₄ and C₂H₂/CO₂ separations in metal-organic frameworks[J]. Angewandte Chemie International Edition, 2023, 62(10): e202217839.
[9]	Du T, Huang L J, Wang J, et al. Luminescent metal-organic frameworks (LMOFs): an emerging sensing platform for food quality and safety control[J]. Trends in Food Science & Technology, 2021, 111: 716-730.
[10]	Qian X K, Yadian B L, Wu R B, et al. Structure stability of metal-organic framework MIL-53(Al) in aqueous solutions[J]. International Journal of Hydrogen Energy, 2013, 38(36): 16710-16715.
[11]	Zhang L, Wu H B, Madhavi S, et al. Formation of Fe₂O₃ microboxes with hierarchical shell structures from metal-organic frameworks and their lithium storage properties[J]. Journal of the American Chemical Society, 2012, 134(42): 17388-17391.
[12]	Zhuang J L, Kind M, Grytz C M, et al. Insight into the oriented growth of surface-attached metal-organic frameworks: surface functionality, deposition temperature, and first layer order[J]. Journal of the American Chemical Society, 2015, 137(25): 8237-8243.
[13]	Bauer C A, Timofeeva T V, Settersten T B, et al. Influence of connectivity and porosity on ligand-based luminescence in zinc metal-organic frameworks[J]. Journal of the American Chemical Society, 2007, 129(22): 7136-7144.
[14]	张军, 楚超霞, 周虎. 一种新型金属有机骨架化合物[Co₃(Hbdc)₂(bdc)₂]·4DMF·2H₂O的合成、表征与晶体结构[J]. 江苏科技大学学报(自然科学版), 2014, 28(4): 342-345.
	Zhang J, Chu C X, Zhou H. Synthesis, characterization and crystal structure of a new metal-organic framework [Co₃(Hbdc)₂(bdc)₂]·4DMF·2H₂O[J]. Journal of Jiangsu University of Science and Technology (Natural Science Edition), 2014, 28(4): 342-345.
[15]	Shen J, He X, Ke T, et al. Simultaneous interlayer and intralayer space control in two-dimensional metal-organic frameworks for acetylene/ethylene separation[J]. Nature Communications, 2020, 11(1): 6259.
[16]	Gu Y M, Yuan Y Y, Chen C L, et al. Fluorido-bridged robust metal-organic frameworks for efficient C₂H₂/CO₂ separation under moist conditions[J]. Chemical Science, 2023, 14(6): 1472-1478.
[17]	Zhu W F, Wang L Z, Liang W J, et al. Bimetallic MOF-74-based mixed matrix membrane for efficient CO₂ separation[J]. Microporous and Mesoporous Materials, 2024, 379: 113288.
[18]	Wang N Y, Mundstock A, Liu Y, et al. Amine-modified Mg-MOF-74/CPO-27-Mg membrane with enhanced H₂/CO₂ separation[J]. Chemical Engineering Science, 2015, 124: 27-36.
[19]	Kazemi A, Ashourzadeh Pordsari M, Tamtaji M, et al. Eco-friendly synthesis and morphology control of MOF-74 for exceptional CO₂ capture performance with DFT validation[J]. Separation and Purification Technology, 2025, 361(1): 131328.
[20]	Fu M, Liu Y L, Lyu Q, et al. Sustainable vapor-phase deposition and applications of MOF films and membranes: a critical review[J]. Separation and Purification Technology, 2025, 356(part A): 129883.
[21]	Zhang Y M, Yin B H, Huang L Z, et al. MOF membranes for gas separations[J]. Progress in Materials Science, 2025, 151: 101432.
[22]	Wasik D O, Vicent-Luna J M, Luna-Triguero A, et al. The impact of metal centers in the M-MOF-74 series on carbon dioxide and hydrogen separation[J]. Separation and Purification Technology, 2024, 339: 126539.
[23]	Lee D J, Li Q M, Kim H, et al. Preparation of Ni-MOF-74 membrane for CO₂ separation by layer-by-layer seeding technique[J]. Microporous and Mesoporous Materials, 2012, 163: 169-177.
[24]	Li Y S, Liang F Y, Bux H, et al. Zeolitic imidazolate framework ZIF-7 based molecular sieve membrane for hydrogen separation[J]. Journal of Membrane Science, 2010, 354(1/2): 48-54.
[25]	Huang A S, Liu Q, Wang N Y, et al. Highly hydrogen permselective ZIF-8 membranes supported on polydopamine functionalized macroporous stainless-steel-nets[J]. Journal of Materials Chemistry A, 2014, 2(22): 8246-8251.
[26]	Li W B, Su P C, Zhang G L, et al. Preparation of continuous NH₂-MIL-53 membrane on ammoniated polyvinylidene fluoride hollow fiber for efficient H₂ purification[J]. Journal of Membrane Science, 2015, 495: 384-391.
[27]	Jia M M, Feng Y, Liu S C, et al. Graphene oxide gas separation membranes intercalated by UiO-66-NH₂ with enhanced hydrogen separation performance[J]. Journal of Membrane Science, 2017, 539: 172-177.
[28]	Liu Y, Jia H P, Wang N, et al. Remarkably enhanced gas separation by partial self-conversion of a laminated membrane to metal-organic frameworks[J]. Angewandte Chemie International Edition, 2015, 54(10): 3028-3032.
[29]	Jin H, Wollbrink A, Yao R, et al. A novel CAU-10-H MOF membrane for hydrogen separation under hydrothermal conditions[J]. Journal of Membrane Science, 2016, 513: 40-46.
[30]	Brown A J, Johnson D J R, Lydon M E, et al. Continuous polycrystalline zeolitic imidazolate framework-90 membranes on polymeric hollow fibers[J]. Angewandte Chemie International Edition, 2012, 51(42): 10615-10618.
[31]	Knebel A, Friebe S, Bigall N C, et al. Comparative study of MIL-96(Al) as continuous metal-organic frameworks layer and mixed-matrix membrane[J]. ACS Applied Materials & Interfaces, 2016, 8(11): 7536-7544.
[32]	Zhou Z M, Wu C, Zhang B Q. ZIF-67 membranes synthesized on α-Al₂O₃-plate-supported cobalt nanosheets with amine modification for enhanced H₂/CO₂ permselectivity[J]. Industrial & Engineering Chemistry Research, 2020, 59(7): 3182-3188.