Constructing nano-composite nanofiltration membranes by in-situ growth: membrane preparation and application

doi:10.11949/0438-1157.20250185

Abstract

Abstract:

The growth of the population and the advancement of industrialization have made the harmless treatment and resource utilization of industrial waste liquid a major challenge facing today's society. As a green, efficient, and environmentally friendly membrane separation technology, nanofiltration technology demonstrates great potential for industrial waste liquid treatment. However, in practical applications, traditional nanofiltration membranes are generally restricted by the "trade-off" effect between selectivity and permeability, as well as the problem of membrane fouling. In recent years, the introduction of nanomaterials with excellent physical and chemical properties into nanofiltration membranes has provided new ideas for solving the above-mentioned problems. This paper reviews the nanomaterials used in the preparation of nano-composite membranes, with a particular focus on the application of in-situ growth in the construction of separation layers or functional layers formed by nanomaterials in nanofiltration membranes. It elaborates in detail on its preparation strategies, structure regulation mechanisms, and performance optimization mechanisms, and introduces the application progress of the prepared nano-composite nanofiltration membranes in the treatment of industrial waste liquid. The aim is to provide theoretical guidance and technical reference for the design and preparation of high-performance composite nanofiltration membranes, and to promote technological innovation and industrial applications in this field.

Key words: in-situ growth, membrane, nanomaterials, nano-composite nanofiltration membrane

摘要：

人口的增长和工业化进程的推进使工业废液的无害化处理及资源化利用成为当今社会面临的重大挑战。纳滤技术作为一项绿色高效、环境友好的膜分离技术，在工业废液处理领域展现出巨大的应用潜力。然而，传统纳滤膜在实际应用中普遍受到选择性与渗透性之间的“trade-off”效应以及膜污染问题的制约。近年来，将具有优异物理化学性质的纳米材料引入纳滤膜中，为解决上述问题提供了新的思路。本文综述了用于纳米复合膜制备的纳米材料，重点聚焦于原位生长在纳滤膜中构筑纳米分离层或功能层中的应用，详细阐述了其制备策略、结构调控机制及性能优化机制，并介绍了所制备的纳米复合纳滤膜在工业废液处理中的应用进展，以期为高性能复合纳滤膜的设计与制备提供理论指导和技术参考，推动该领域的技术创新与工业应用。

关键词: 原位生长, 膜, 纳米材料, 纳米复合纳滤膜

CLC Number:

TQ 028.3

Yu WANG, Yingnan FENG, Tao WANG, Zhiping ZHAO. Constructing nano-composite nanofiltration membranes by in-situ growth: membrane preparation and application[J]. CIESC Journal, 2025, 76(9): 4723-4736.

王钰, 冯英楠, 王涛, 赵之平. 原位生长构筑纳米复合纳滤膜：膜制备与应用[J]. 化工学报, 2025, 76(9): 4723-4736.

Figures/Tables 10

Fig.1 Schematic diagram of the separation mechanism of nanofiltration membrane

Fig.2 Preparation and application of nano-composite nanofiltration membranes constructed by in-situ growth

Fig.3 Schematic illustration for preparation of ZIF-8/WS2 composite membrane[37]

Fig.4 Formation and structure of the membranes: (a) Schematic illustration of membrane fabrication process by synergistic in-situ MOF growth method; Surface SEM images of PES substrate (b), Co2+@PPN (c) and ZIF-67@PPN1 membranes (d); Cross-section SEM images of PES substrate (e), Co2+@PPN (f) and ZIF-67@PPN1 membranes (g)[38]

Table 1 Separation performance comparison of composite NF membranes with nanomaterial separation layers fabricated viain-situ growth

膜应用场景	纳米材料	溶剂	分离性能（通量/选择性）	文献
纳滤	GO/Co(OH)₂纳米片	水	17.0 L·m^-2·h^-1/ $R N a 2 S O 4$ >91%	[58]
有机溶剂纳滤	HKUST-1	丙酮	80 L·m^-2·h^-1·bar^-1/MWCO=794	[36]
	ZIF-8	异丙醇	272 L·m^-2·h^-1·bar^-1/R_刚果红=99%	[37]
	MoS₂	甲醇	40.3 L·m^-2·h^-1·bar^-1/R_伊文思蓝=98.1%	[56]
	MoS₂	甲醇	52.2 L·m^-2·h^-1·bar^-1/R_铬黑T>97%	[57]
	α-Co(OH)₂纳米片	甲醇	127 L·m^-2·h^-1·bar^-1/R_铬黑T=96%	[59]
	聚苯胺	乙醇	14.9 L·m^-2·h^-1·bar^-1/R_孟加拉红=98.1%	[60]
	COF	乙醇	98.4 L·m^-2·h^-1·bar^-1/MWCO=784	[61]
疏松纳滤	ZIF-67	水	45.68 L·m^-2·h^-1·bar^-1/R_刚果红=99.98%	[38]
	ZIF-8	水	45 L·m^-2·h^-1·bar^-1/R_铬黑T=99%	[39]
	COF	水	282 L·m^-2·h^-1·bar^-1/R_刚果红=99.8%	[53]
	COF-300	水	79.1 L·m^-2·h^-1·bar^-1/R_铬黑T=99.4%	[54]
	GO	水	493.9 L·m^-2·h^-1·bar^-1/R_刚果红>99%	[62]
	层状双氢氧化合物	水	19.8 L·m^-2·h^-1·bar^-1/R_甲基蓝=97.9%	[63]
	共价三嗪框架	水	44.8 L·m^-2·h^-1·bar^-1/R_铬黑T>97%	[64]

Table 1 Separation performance comparison of composite NF membranes with nanomaterial separation layers fabricated viain-situ growth

膜应用场景	纳米材料	溶剂	分离性能（通量/选择性）	文献
纳滤	GO/Co(OH)₂纳米片	水	17.0 L·m^-2·h^-1/ $R N a 2 S O 4$ >91%	[58]
有机溶剂纳滤	HKUST-1	丙酮	80 L·m^-2·h^-1·bar^-1/MWCO=794	[36]
	ZIF-8	异丙醇	272 L·m^-2·h^-1·bar^-1/R_刚果红=99%	[37]
	MoS₂	甲醇	40.3 L·m^-2·h^-1·bar^-1/R_伊文思蓝=98.1%	[56]
	MoS₂	甲醇	52.2 L·m^-2·h^-1·bar^-1/R_铬黑T>97%	[57]
	α-Co(OH)₂纳米片	甲醇	127 L·m^-2·h^-1·bar^-1/R_铬黑T=96%	[59]
	聚苯胺	乙醇	14.9 L·m^-2·h^-1·bar^-1/R_孟加拉红=98.1%	[60]
	COF	乙醇	98.4 L·m^-2·h^-1·bar^-1/MWCO=784	[61]
疏松纳滤	ZIF-67	水	45.68 L·m^-2·h^-1·bar^-1/R_刚果红=99.98%	[38]
	ZIF-8	水	45 L·m^-2·h^-1·bar^-1/R_铬黑T=99%	[39]
	COF	水	282 L·m^-2·h^-1·bar^-1/R_刚果红=99.8%	[53]
	COF-300	水	79.1 L·m^-2·h^-1·bar^-1/R_铬黑T=99.4%	[54]
	GO	水	493.9 L·m^-2·h^-1·bar^-1/R_刚果红>99%	[62]
	层状双氢氧化合物	水	19.8 L·m^-2·h^-1·bar^-1/R_甲基蓝=97.9%	[63]
	共价三嗪框架	水	44.8 L·m^-2·h^-1·bar^-1/R_铬黑T>97%	[64]

Fig.5 Schematic of membrane fabrication: ZIF-8 synthesis (a), LBL fabrication procedures (b), and cross-sectional structure of the PA/ZIF-8 (LBL) membrane (c)[65]

Fig.6 Schematic illustration of as-prepared TFN membranes with two prepared strategies[66]

Fig.7 SEM images of the top surfaces and cross sections of prepared membranes and water permeability and salt rejection[66]

Fig.8 Schematic diagram of the fabrication processes for three types of TFC membranes based on PVDF substrates[68]

Table 2 Separation performance comparison of composite NF membranes with nanomaterial interlayers fabricated by in-situ growth

膜应用场景	纳米材料	溶剂	分离性能（通量/选择性）	文献
纳滤	ZIF-8	水	9 L·m^-2·h^-1·bar^-1/R_刚果红>99.8%	[65]
	ZIF-8	水	29.4 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ =94%	[66]
	UiO-66-NH₂	水	11.55 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ =92.97%	[67]
	CD-MOF	水	29.4 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ >99%	[71]
	ZIF-8	水	31.4 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ =96.3%	[72]
有机溶剂纳滤	Cu-TCPP	乙醇	1.93 L·m^-2·h^-1·bar^-1/R_刚果红＞99.3%	[68]
有机溶剂纳滤	HKUST-1	甲醇	9.59 L·m^-2·h^-1·bar^-1/R_亮蓝G250=98.8%	[73]
疏松纳滤	TiO₂	水	65.0 L·m^-2·h^-1·bar^-1/R_刚果红>95%	[69]
	ZnO	水	375 L·m^-2·h^-1·bar^-1/R_刚果红>91%	[70]
	Zn-IL	水	26.5 L·m^-2·h^-1·bar^-1/R_甲基蓝=99%	[74]
	ZnO	水	21 L·m^-2·h^-1·bar^-1/R_{双氯芬酸钠}>90%	[75]

Table 2 Separation performance comparison of composite NF membranes with nanomaterial interlayers fabricated by in-situ growth

膜应用场景	纳米材料	溶剂	分离性能（通量/选择性）	文献
纳滤	ZIF-8	水	9 L·m^-2·h^-1·bar^-1/R_刚果红>99.8%	[65]
	ZIF-8	水	29.4 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ =94%	[66]
	UiO-66-NH₂	水	11.55 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ =92.97%	[67]
	CD-MOF	水	29.4 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ >99%	[71]
	ZIF-8	水	31.4 L·m^-2·h^-1·bar^-1/ $R N a 2 S O 4$ =96.3%	[72]
有机溶剂纳滤	Cu-TCPP	乙醇	1.93 L·m^-2·h^-1·bar^-1/R_刚果红＞99.3%	[68]
有机溶剂纳滤	HKUST-1	甲醇	9.59 L·m^-2·h^-1·bar^-1/R_亮蓝G250=98.8%	[73]
疏松纳滤	TiO₂	水	65.0 L·m^-2·h^-1·bar^-1/R_刚果红>95%	[69]
	ZnO	水	375 L·m^-2·h^-1·bar^-1/R_刚果红>91%	[70]
	Zn-IL	水	26.5 L·m^-2·h^-1·bar^-1/R_甲基蓝=99%	[74]
	ZnO	水	21 L·m^-2·h^-1·bar^-1/R_{双氯芬酸钠}>90%	[75]

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