Ni-MOF-74金属有机框架膜的结构调变及气体分离性能研究

doi:10.11949/0438-1157.20241522

摘要/Abstract

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

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

中图分类号:

TQ 028.8

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.

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.

图/表 9

图1 气体分离测试装置示意图

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

图2 金属离子与配体配比对Ni-MOF-74膜晶相结构的影响

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

图3 金属离子与配体的配比对Ni-MOF-74膜微观形貌结构的影响

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

图4 Ni-MOF-74粉末的氮气等温吸附-脱附曲线（插图为孔径分布图）

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

图5 Ni-MOF-74粉体的DTG-TGA曲线

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

表1 Ni-MOF-74膜的单气体渗透与理想选择性

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

图6 不同Ni-MOF-74膜的CO2渗透性

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

图7 Ni-MOF-74膜（4∶1）的渗透性能与渗透分子直径的关系（插图为理想选择性和分离因子对比）

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)

表2 不同MOF分离膜分离性能对比

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

表2 不同MOF分离膜分离性能对比

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

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