Recent progress on metal-organic framework membranes towards uranium separation from seawater

doi:10.11949/0438-1157.20241307

Abstract

Abstract:

The oceans hold ca. 4.5 billion tons of uranium, which will provide sustainable production for the global nuclear industry more than thousands of years. Therefore, uranium extraction from seawater is considered as one of the world-changing chemical separation technologies. Membrane separation is widely used for uranium extraction from seawater because of its high efficiency, low energy consumption, and non-pollution. Metal-organic framework (MOF) holds great potential for seawater uranium extraction with membrane technology due to the tunable pore size, rich functionality, and diverse post-modification protocols. This paper reviews the latest research progress and future development direction of membrane separation technology in uranium extraction from seawater, and especially systematically summarizes the separation mechanism and challenges of uranium extraction from seawater using MOF membranes.

Key words: uranium extraction, metal-organic framework (MOF), membrane separation, adsorption, filtration, membrane

摘要：

海洋中约有45亿吨铀，能够满足全球核工业生产千年以上的可持续生产需求，因此海水提铀被认为是改变世界的化学分离技术之一；膜分离因效率高、能耗低、无污染等特点，被广泛用于海水提铀。金属有机骨架（MOF）由于其可变的孔道结构、丰富的活性位点、化学修饰多样性，作为膜材料在海水提铀应用领域前景广阔。综述了将膜分离技术应用于海水提铀的最新研究进展与未来发展方向，系统总结了采用MOF膜实现海水提铀的分离机理与面临的挑战。

关键词: 海水提铀, 金属有机骨架, 膜分离, 吸附, 过滤, 膜

CLC Number:

TQ 028.3

Yue ZHANG, Jiaxin LIU, Jing MA, Yi LIU. Recent progress on metal-organic framework membranes towards uranium separation from seawater[J]. CIESC Journal, 2025, 76(5): 2087-2100.

张越, 刘佳鑫, 马敬, 刘毅. 金属有机骨架膜应用于海水提铀研究进展[J]. 化工学报, 2025, 76(5): 2087-2100.

Figures/Tables 14

Fig.1 (a) Nuclear power for electricity generation; (b) Nuclear power for hydrogen production; (c) Nuclear power for seawater desalination[3]

Fig.2 (a) World nuclear power unit development requirements; (b) World nuclear power development requirements in the regional distribution[3]

Fig.3 Major ion concentrations in seawater[9, 12]

Fig.4 (a) Effect of different salinities on the absorption of uranium by adsorbents[42]; (b) Distribution of U(Ⅵ) in different pH ranges[42, 49]

Fig.5 Timeline of the development of functional materials that have been used in seawater separation of uranium since 1964[20, 39,57]

Fig.6 (a) Synthesis of ZIF-67; (b) Schematic of the mechanism for U(Ⅵ) separation by ZIF-67 adsorption[60]

Fig.7 (a) Schematic diagram of the preparation process for UiO-66@PAO membrane; (b) Schematic diagram of the chemical structure for UiO-66@PAO and the process of selective adsorption of uranium by UiO-66@PAO MOF-based membrane[67]

Fig.8 (a) Schematic of SEM and U(Ⅵ) capture and release by microporous polyamide membranes[78]; (b) Schematic of U(Ⅵ) capture by LAM membranes in natural seawater[80]

Fig.9 Schematic diagram of the U(Ⅵ) extraction and antifouling process for amines in natural seawater[84]

Table 1 Size of UO22+，Fe3+，Ca2+，Mg2+，Na+，K+，Cl-，H2O in the seawater[88-90]

离子(分子)种类	水合离子(分子)直径/Å
$U O 2 2 +$	11.6
$F e 3 +$	9.1
$M g 2 +$	8.6
$C a 2 +$	8.2
$N a +$	7.2
$K +$	6.6
$C l -$	6.6
$H 2 O$	2.8

Table 1 Size of UO22+，Fe3+，Ca2+，Mg2+，Na+，K+，Cl-，H2O in the seawater[88-90]

离子(分子)种类	水合离子(分子)直径/Å
$U O 2 2 +$	11.6
$F e 3 +$	9.1
$M g 2 +$	8.6
$C a 2 +$	8.2
$N a +$	7.2
$K +$	6.6
$C l -$	6.6
$H 2 O$	2.8

Fig.10 (a) Schematic diagram of MOF-808 membrane prepared by direct growth method[91]; (b) Schematic diagram of ZIF-8 membrane prepared by reverse diffusion interfacial growth method[93]; (c) Schematic diagram of MIL-125(Cu) membrane prepared by secondary growth method[92]; (d) Schematic diagram of ZIF-8 membrane prepared by rapid thermal deposition method[94]

Fig.11 (a) Schematic diagram of ZIF-8-PCTM membrane preparation and separation; (b) Schematic diagram of the preparation process of TAPP-ZIF-60 membrane; (c) SEM image of the surface of ZIF-8-PCTM membrane; (d) SEM image of the interface of ZIF-8-PCTM membrane[95]; (e) Effect of high concentration of coexisting ions in simulated seawater on the uranium rejection rate of TAPP-ZIF-60; (f) Effect of high concentration of co-existing ions in natural seawater on the uranium rejection rate of TAPP-ZIF-6[96]

Table 2 Separation performance of MOF membranes for U（Ⅵ） in simulated seawater

序号	材料	吸附容量/（mg/g）	时间/h	方法	文献
1	MOF-808-PO	100	0.33	adsorption	[99]
2	MOF-3	109	2.50	adsorption	[97]
3	NU-1000-PO	110	0.33	adsorption	[99]
4	Zn(HBTC)(L)(H₂O)₂	115	0.08	adsorption	[102]
5	Co-SLUG-35	118	4.00	adsorption	[103]
6	MOF-2	217	1.00	adsorption	[97]
7	MOF-5	237.0	0.08	adsorption	[98]
8	PCN-222-PA	401.6	0.50	adsorption	[79]
9	MUU	475	4.00	adsorption	[104]
10	GZA	602.41	2.00	adsorption	[100]
11	HKUST-1	840.3	2.00	adsorption	[101]
12	ZIF-67	1683.8	2.50	adsorption	[60]

Table 3 Separation performance and cycle times of MOF membranes for U（‍Ⅵ） in natural seawater

序号	材料	吸附容量	循环次数	方法	文献
1	ZIF-8	62.30 mg/g	7	adsorption	[95]
2	SSUP	12.33 mg/g	6	adsorption	[105]
3	W-UiO-66	6.20 mg/g	5	adsorption	[20]
3	UiO-66-NH₂@CS-PDA	5.52 mg/g	5	adsorption	[82]
4	UiO-66-NH₂	5.52 mg/g	10	adsorption	[82]
5	UiO-66-AO	5.20 mg/g	4	adsorption	[73]
6	ZIF-90-ABOA	2.80 mg/g	5	adsorption	[106]
7	HF-PEI-GDAC	3.34 μg/L	5	adsorption	[107]
8	MIL-101-AO	3.30 μg/L	5	adsorption	[108]

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