金属有机骨架混合基质水处理分离膜研究进展

doi:10.16085/j.issn.1000-6613.2020-0744

摘要/Abstract

摘要：

金属有机骨架（MOFs）晶体由无机金属离子和有机配体通过自组装合成，具有高的孔隙率和可调节的窗口尺寸，可使MOFs混合基质膜在水处理时同步获得高通量和高截留率，有望突破传统分离膜的渗透性和选择性之间此消彼长的trade-off效应。本文综述了MOFs的典型构造、影响MOFs混合基质膜性能的关键因素、MOFs混合基质膜的制备方法、MOFs颗粒改善混合基质膜水传输和溶质分离性能的原理以及MOFs混合基质膜在水处理微滤/超滤、纳滤/反渗透和正渗透领域的最新研究进展。最后总结了MOFs混合基质膜在水处理领域的未来发展亟待解决的关键问题，主要包括高性能、低成本膜的可控制备、膜结构和性能之间定量构效关系的深入探索以及如何拓宽其应用范围等，对加快MOFs混合基质膜的产业化进程具有指导意义。

关键词: 膜, 分离, 渗透性, 选择性, 金属有机骨架

Abstract:

Metal organic frameworks (MOFs) synthesized by self-assembly of inorganic metal ions and organic ligands with high porosity and adjustable window size endow the MOFs mixed matrix membranes with both high flux and high rejection, which are expected to break the trade-off effect between permeability and selectivity of traditional membranes. This paper reviews the typical structures of MOFs, the preparation methods and the key influence factors of the performance of the MOFs mixed matrix membranes, and the principle of MOFs nanoparticles for improving the water transport and solute separation performance. Besides, the latest research progresses of the MOFs mixed matrix membranes in the fields of microfiltration/ultrafiltration, nanofiltration/reverse osmosis, and forward osmosis for water treatment are introduced. Finally, several critical issues in the future development of the MOFs mixed matrix membranes for water treatment are summarized, mainly including the controllable preparation of the membranes with high-performance and low-cost, the deep exploration of the quantitative structure-function relationship between membrane structure and performance, and the expanding of their application scopes, which have guiding significance for speeding up the industrialization process of the MOFs mixed matrix membranes.

Key words: membranes, separation, permeability, selectivity, metal organic frameworks

中图分类号:

TB333

赵东升. 金属有机骨架混合基质水处理分离膜研究进展[J]. 化工进展, 2021, 40(2): 1035-1047.

Dongsheng ZHAO. Recent advances in metal organic frameworks mixed matrix membranes for water treatment[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 1035-1047.

图/表 10

图1 影响MOFs混合基质水处理分离膜性能的关键因素

图2 自组装界面反应法制备ZIF-8/聚乙烯亚胺混合基质膜的步骤[28]

图3 MOFs在混合基质膜中的水快速传输通道和尺寸筛分作用

表1 MOFs混合基质微滤/超滤膜在水处理中的应用

膜的分类	MOFs混合基质膜	进料液	渗透性 /L·m^-2·h^-1·bar^-1	分离的溶质，分离性能	改善水传输和溶质分离性能的原理	参考文献
微滤	ZIF-8/聚四氟乙烯膜	纯水	54800	黄体酮，约95%	水分子与疏水性ZIF-8内壁的摩擦低，膜孔隙率增大，ZIF-8表面N-H与水分子通过氢键结合形成水的快速传输通道；黄体酮与ZIF-8的特异性相互作用和氢键形成	[54]
超滤	聚磺基甲基丙烯酸酯功能化UiO-66/聚砜膜	纯水	301	牛血清白蛋白，>98%	膜面亲水性改善，膜孔隙率增大，功能化UiO-66的多孔结构及其与聚砜基质之间的微间隙为水分子的通过提供额外的传输通道	[30]
超滤	亲水性中空ZIF-8/ 聚砜膜	纯水	298.5	牛血清白蛋白，>98%	膜面亲水性改善，膜结构均匀，亲水中空ZIF-8的多孔结构为水分子提供额外的优先传输通道	[51]
超滤	聚丙烯酸/ZIF-8/ 聚偏氟乙烯膜	纯水	460	[Ni²⁺]₀=2mg/L， <0.1mg/L	Ni²⁺与ZIF-8的羟基及聚丙烯酸层的羧基之间的静电吸引和氢键作用	[55]
超滤	F300、A100和C300/ 聚丙烯腈膜	纯水	182、230和261	葡萄聚糖，>98%	水溶性去除部分MOFs增强膜孔隙的连通性，提高膜的孔隙率	[37]
超滤	HKUST-1/聚醚砜膜	纯水	490	牛血清白蛋白，约96%	水溶性去除HKUST-1，提高膜的孔隙率，为水分子创造额外的传输通道，降低传输阻力；膜的尺寸筛分效应及与牛血清白蛋白之间强静电排斥作用，使其保持较高的截留性能	[38]

图4 MOFs混合基质聚丙烯腈超滤膜的孔隙率和性能变化[37]

表2 MOFs混合基质纳滤/反渗透膜在水处理中的应用

膜的分类	MOFs混合基质膜	进料液	渗透性 /L·m^-2·h^-1·bar^-1	分离的溶质，分离性能	改善水传输和溶质分离性能的原理	参考文献
纳滤	UiO-66/聚酰胺膜	纯水	11.5	SeO $3 2 -$ 、SeO $4 2 -$ 和HAsO $4 2 -$ ，96.5%、97.4%和98.6%	膜面亲水性改善，引入多孔性的水分子通道，分离层厚度减小；膜的平均孔径减小，孔径分布变窄，表面负电荷改善增强	[24]
纳滤	聚苯乙烯磺酸钠改性ZIF/聚酰胺膜	纯水	14.9	活性黑5和活性蓝2， >99%	膜面亲水性提高，聚酰胺层交联度下降，纳米颗粒自身的孔隙及其与聚酰胺之间的间隙为水分子快速传输提供通道；空间位阻和对荷负电染料分子的静电排斥作用增强	[42]
纳滤	氨基化UiO-66/ 聚酰胺膜	1500mg·L^-1Na₂SO₄	30.8	Na₂SO₄，97.5%	改善膜的亲水性，形成渔网状褶皱结构增大有效过滤面积，增加水分子的传输通道	[48]
纳滤	聚苯乙烯磺酸钠/HKUST-1膜	—	—	Li⁺、Na⁺、K⁺和Mg²⁺，Li⁺/Na⁺=35、Li⁺/K⁺=67和Li⁺/Mg²⁺=1815	水合离子直径的不同及其与磺酸基团亲合性的差异	[56]
纳滤	MIL-101(Cr) /聚酰胺膜	纯水	39.5	内分泌干扰物：羟苯甲酯、羟苯丙酯、羟苯甲酯和双酚A，47.4%、45.9%、51.1%和79.8%	MIL-101(Cr)的孔窗作为亲水选择性纳米通道增强水分子的传输速率；通过抑制疏水相互作用增强对疏水内分泌干扰物的去除	[52]
纳滤	MIL-53(Al)、NH₂-UiO-66、 ZIF-8/聚酰胺膜	10mmol·L^-1NaCl和50μg·L^-1药物	7.2	药物：萘啶酸、磺胺甲唑、舒必利，>80%、 >80%、>90%	MOFs独特的通道促进水分子的传输；MOFs大小孔窗的选择性屏障作用，维持膜的选择性；降低聚酰胺层的交联度，膜面羧基含量增大，增强对荷负电溶质的静电排斥作用	[53]
纳滤	PD/ZIF-8/聚酰胺膜	1000mg·L^-1Na₂SO₄	53.5	Na₂SO₄，>95%	通过控制模板MOFs的负载量和粒径，对聚酰胺层的表面形貌和表面积进行微调，形成具有褶皱形貌的聚酰胺层，增大高渗透性有效过滤面积	[39]
反渗透	ZIF-8/聚酰胺膜	2000mg·L^-1NaCl	3.35	NaCl，98.5%	降低聚酰胺层的交联度，水在疏水性ZIF-8纳米受限通道内的摩擦阻力低，有利于其快速传输；ZIF-8的咪唑酯连接增强与聚酰胺基质的相容性，保证高的截留率	[62]
反渗透	MIL-101(Cr)/ 聚酰胺膜	2000mg·L^-1NaCl	2.2	NaCl，>99%	MIL-101(Cr)的多孔结构在致密的聚酰胺层中建立直接的水通道；MIL-101(Cr)与聚酰胺层的相容性好，两者紧密结合，从而表现出高的截留率	[63]

表2 MOFs混合基质纳滤/反渗透膜在水处理中的应用

膜的分类	MOFs混合基质膜	进料液	渗透性 /L·m^-2·h^-1·bar^-1	分离的溶质，分离性能	改善水传输和溶质分离性能的原理	参考文献
纳滤	UiO-66/聚酰胺膜	纯水	11.5	SeO $3 2 -$ 、SeO $4 2 -$ 和HAsO $4 2 -$ ，96.5%、97.4%和98.6%	膜面亲水性改善，引入多孔性的水分子通道，分离层厚度减小；膜的平均孔径减小，孔径分布变窄，表面负电荷改善增强	[24]
纳滤	聚苯乙烯磺酸钠改性ZIF/聚酰胺膜	纯水	14.9	活性黑5和活性蓝2， >99%	膜面亲水性提高，聚酰胺层交联度下降，纳米颗粒自身的孔隙及其与聚酰胺之间的间隙为水分子快速传输提供通道；空间位阻和对荷负电染料分子的静电排斥作用增强	[42]
纳滤	氨基化UiO-66/ 聚酰胺膜	1500mg·L^-1Na₂SO₄	30.8	Na₂SO₄，97.5%	改善膜的亲水性，形成渔网状褶皱结构增大有效过滤面积，增加水分子的传输通道	[48]
纳滤	聚苯乙烯磺酸钠/HKUST-1膜	—	—	Li⁺、Na⁺、K⁺和Mg²⁺，Li⁺/Na⁺=35、Li⁺/K⁺=67和Li⁺/Mg²⁺=1815	水合离子直径的不同及其与磺酸基团亲合性的差异	[56]
纳滤	MIL-101(Cr) /聚酰胺膜	纯水	39.5	内分泌干扰物：羟苯甲酯、羟苯丙酯、羟苯甲酯和双酚A，47.4%、45.9%、51.1%和79.8%	MIL-101(Cr)的孔窗作为亲水选择性纳米通道增强水分子的传输速率；通过抑制疏水相互作用增强对疏水内分泌干扰物的去除	[52]
纳滤	MIL-53(Al)、NH₂-UiO-66、 ZIF-8/聚酰胺膜	10mmol·L^-1NaCl和50μg·L^-1药物	7.2	药物：萘啶酸、磺胺甲唑、舒必利，>80%、 >80%、>90%	MOFs独特的通道促进水分子的传输；MOFs大小孔窗的选择性屏障作用，维持膜的选择性；降低聚酰胺层的交联度，膜面羧基含量增大，增强对荷负电溶质的静电排斥作用	[53]
纳滤	PD/ZIF-8/聚酰胺膜	1000mg·L^-1Na₂SO₄	53.5	Na₂SO₄，>95%	通过控制模板MOFs的负载量和粒径，对聚酰胺层的表面形貌和表面积进行微调，形成具有褶皱形貌的聚酰胺层，增大高渗透性有效过滤面积	[39]
反渗透	ZIF-8/聚酰胺膜	2000mg·L^-1NaCl	3.35	NaCl，98.5%	降低聚酰胺层的交联度，水在疏水性ZIF-8纳米受限通道内的摩擦阻力低，有利于其快速传输；ZIF-8的咪唑酯连接增强与聚酰胺基质的相容性，保证高的截留率	[62]
反渗透	MIL-101(Cr)/ 聚酰胺膜	2000mg·L^-1NaCl	2.2	NaCl，>99%	MIL-101(Cr)的多孔结构在致密的聚酰胺层中建立直接的水通道；MIL-101(Cr)与聚酰胺层的相容性好，两者紧密结合，从而表现出高的截留率	[63]

图5 聚苯乙烯磺酸钠@HKUST-1混合基质膜对二元混合离子选择性、水合离子直径及与磺酸基团的亲合性[56]

表3 PD/ZIF-8模板纳滤膜与最新报道纳滤膜的总体性能比较

膜的类型	渗透性/L·m^-2·h^-1·bar^-1	Na₂SO₄截留率/%	参考文献
PD/ZIF-8模板纳滤膜(PIP/PD/ZIF-8-TMC)	53.5	>95.0	[39]
TFN(PIP/MoS₂-TMC)	7.8	94.4	[64]
NFM-15(PIP-TMC)	23.7	99.4	[65]
NFM-4(PIP-TMC/TAC)	13.2	97.6	[66]
CS(PIP-TMC)	10.1	89.1	[67]
M-50(PIP-TMC)	26.2	97.7	[68]
CNC-TFC-M2(PIP-CNCs/TMC)	16.2	98.8	[69]
Dow NF-270	11.6	94.0	[70]

表4 MOFs混合基质正渗透膜在水处理中的应用

MOFs混合基质膜	进料液	汲取液	运行模式	渗透通量 /L·m^-2·h^-1	比盐通量 /g·L^-1	改善膜渗透选择性的原理	参考文献
UiO-66/聚酰胺膜	纯水	1mol·L^-1 NaCl	活性层-汲取液	36.7	0.20	膜面亲水性提高，UiO-66的小孔径限制高浓度汲取液的溶质反向通量，缓解内部浓差极化，提高净渗透驱动力	[50]
3HBTC/聚酰胺膜	纯水	2mol·L^-1 NaCl	活性层-汲取液	82	0.13	3HBTC的嵌入使聚合物链填充中断，降低聚酰胺层的交联度，增强膜面亲水性，吸引水分子并降低其传输阻力	[74]
UiO-66/磺化聚砜/聚砜膜	纯水	1.25mol·L^-1 Na₂SO₄	—	88.3	0.12	亚纳米孔径的增强微孔，使UiO-66基吸附和离子筛分特性直接转化，消除渗透压驱动下的内部浓度极化	[43]
以F300、A100、C300/聚丙烯腈混合基质膜为基底的聚酰胺膜	纯水	0.5mol·L^-1 MgCl₂	活性层-汲取液	93、 100、 107	0.08、 0.13、 0.17	水溶性去除部分F300、A100和C300，提高基底的孔隙率和亲水性，降低孔曲折程度，正渗透膜的内部浓差极化得到有效改善，膜通量增加；基底孔隙率的增大导致溶质截留率略有下降	[40]

图6 PRO和FO模式下UiO-66负载量对正渗透膜的水通量和盐反向通量的影响[50]

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