Research progress of smart responsive membranes based on novel porous organic polymers

doi:10.11949/0438-1157.20241215

Abstract

Abstract:

Membrane separation technology has been widely used in many fields due to its high efficiency and environmental friendliness. However, traditional membranes have limited adaptability in complex environments and are difficult to meet the ever-increasing separation needs. In contrast, smart responsive membranes can dynamically modify their structure and properties in response to external stimuli, such as light, temperature, pH, or electric fields, offering greater flexibility and improved performance across a wide range of applications. The development of novel porous organic polymers, such as covalent organic frameworks, metal organic frameworks, and conjugated microporous polymers, has paved the way for new possibilities in the design and optimization of these membranes. This review presents recent advancements in smart responsive membranes based on porous organic polymers, with a focus on how different external stimuli influence their structure and performance. Additionally, it explores various fabrication methods, strategies for integrating responsive groups, and addresses potential challenges along with future research directions in the field.

Key words: membrane, separation, smart response, novel organic porous polymers, nanofiltration

摘要：

膜分离技术因其高效与环境友好的特性，在多个领域得到了广泛应用。然而，传统膜在复杂环境中的适应性有限，难以满足不断提升的分离需求。智能响应膜能够响应光、温度、pH、电场等外界刺激，实现膜结构与性能的动态调控，展现出应对多变应用需求的优势。随着共价有机框架、金属有机框架和共轭微孔聚合物等新型有机多孔聚合物的发展，智能响应膜的设计和优化迎来了新的机遇。该综述总结了新型有机多孔聚合物智能响应膜的研究进展，分析了不同外界刺激对膜结构和性能的调控，梳理了制膜方法及响应基团的引入策略，并探讨了未来的发展方向与挑战。

关键词: 膜, 分离, 智能响应, 新型有机多孔聚合物, 纳滤

CLC Number:

TQ 028.8

Yanqiu LU, Yang DI, Wenbo SHI, Congcong YIN, Yong WANG. Research progress of smart responsive membranes based on novel porous organic polymers[J]. CIESC Journal, 2025, 76(5): 2101-2118.

陆艳秋, 狄扬, 石文博, 殷聪聪, 汪勇. 基于新型有机多孔聚合物的智能响应膜研究进展[J]. 化工学报, 2025, 76(5): 2101-2118.

Figures/Tables 11

Fig.1 Schematic representations of typical POPs structures

Fig.2 The scope of this review

Fig.3 Representative responsive groups/moieties

Fig.4 (a) Schematic illustration of the light-switchable structural change of TbDa-Azo membrane [62]; (b) Schematic illustration of light-switchable structural change of the azo-CMP membrane[64]; (c) Schematic illustration of the temperature-switchable structural change of trZT-MOF nanosheet membrane[65]; (d) Schematic illustration of light-gated ion transport through the 2D MOF membrane [67]; (e) Schematic illustration of CC3α structure and CC3γ′ structure formed by soaking in MeOH[68]

Fig.5 (a) Schematic illustration of Na+-responsive controllable emulsion separation through B15C5-coated membranes and contact angles of the as-prepared material without and with Na+[69]; (b) Schematic illustration of the switchable wettability of CC-ZIF-PIL membrane and digital photographs of contact angle and water and oil droplets on the membrane[74]

Fig.6 (a) Schematic illustration of the voltage-gated BABD-CB membrane in the electric field[78]; (b) Schematic illustration of working principle of the electro-controlled Janus membrane[81]; (c) Proposed chemical reactivity features of COF-DT membranes at various pH values and DFT relative energies and charge distribution for the small-molecule model compound for COF-DT in acidic, neutral, and basic conditions[82]; (d) Schematic illustration of switchable Na+/K+ selectivity of COF-Cys membranes[83]

Fig.7 Schematic illustration of photo-responsive COF membrane fabricated by interfacial polymerization[85]

Fig.8 Schematic illustration of TbDa-Azo COF membrane fabricated by solvothermal method[62]

Fig.9 Schematic illustration of the 3DOM ZIF-8-based membrane fabricated by vacuum assisted self-assembly method[66]

Fig.10 Schematic illustration of (CILs@PAR (c-s) CNPs)/PIM MMMs fabricated by blending method[90]

Table 1 Characteristics and applications of smart responsive membranes

响应类型	机理	特点	响应对膜结构的调控优点和缺点	应用范围
光响应	光响应基团通过光致异构化改变膜的孔结构等，实现可控分离	非接触性、可控性强，适用于远程调控；响应速度快，可实现高精度分离	优点：无须外加化学试剂，通过光照方向和强度可灵活调控膜孔结构；缺点：需特定波长光源，长期光照可能导致光响应基团降解，影响膜稳定性	纳滤、气体分离等
温度响应	温敏聚合物通过相转变改变膜的孔结构等，实现可控分离	易操作，可利用环境温度调节，适用于多种应用环境	优点：通过温度可对膜孔径进行调适；缺点：温敏聚合物的长期耐用性较低，可能导致膜性能衰减	纳滤、膜抗污染等
电响应	外加电场通过调控膜表面的电荷分布和密度，实现可控分离	调控精确，响应速度快，适用于高精度分离任务	优点：外加电场可精准调控电荷分布，表面电荷的变化也会引起膜亲疏水性的变化；缺点：电场分布不均可能影响电荷分布	纳滤、油水分离、膜抗污染等
pH响应	酸碱性基团通过电离状态变化调节膜表面电荷密度，实现可控分离	对化学环境变化高度敏感，可灵活调控分离性能；适用于动态离子分离任务	优点：pH变化可显著调节表面电荷密度，提升对带电离子的选择性；缺点：极端pH条件下可导致膜材料降解；酸碱溶液的使用需考虑环保问题	纳滤、脱盐等
离子响应	通过与离子结合或解离，实现可控分离	选择性强，适合特定离子分离；响应行为与分离效果密切相关	优点：可针对特定离子调控膜表面电荷，提升离子选择性，此外，离子与膜的结合对孔径有微调作用；缺点：对离子浓度与类型依赖较高	水处理、资源回收等

Table 1 Characteristics and applications of smart responsive membranes

响应类型	机理	特点	响应对膜结构的调控优点和缺点	应用范围
光响应	光响应基团通过光致异构化改变膜的孔结构等，实现可控分离	非接触性、可控性强，适用于远程调控；响应速度快，可实现高精度分离	优点：无须外加化学试剂，通过光照方向和强度可灵活调控膜孔结构；缺点：需特定波长光源，长期光照可能导致光响应基团降解，影响膜稳定性	纳滤、气体分离等
温度响应	温敏聚合物通过相转变改变膜的孔结构等，实现可控分离	易操作，可利用环境温度调节，适用于多种应用环境	优点：通过温度可对膜孔径进行调适；缺点：温敏聚合物的长期耐用性较低，可能导致膜性能衰减	纳滤、膜抗污染等
电响应	外加电场通过调控膜表面的电荷分布和密度，实现可控分离	调控精确，响应速度快，适用于高精度分离任务	优点：外加电场可精准调控电荷分布，表面电荷的变化也会引起膜亲疏水性的变化；缺点：电场分布不均可能影响电荷分布	纳滤、油水分离、膜抗污染等
pH响应	酸碱性基团通过电离状态变化调节膜表面电荷密度，实现可控分离	对化学环境变化高度敏感，可灵活调控分离性能；适用于动态离子分离任务	优点：pH变化可显著调节表面电荷密度，提升对带电离子的选择性；缺点：极端pH条件下可导致膜材料降解；酸碱溶液的使用需考虑环保问题	纳滤、脱盐等
离子响应	通过与离子结合或解离，实现可控分离	选择性强，适合特定离子分离；响应行为与分离效果密切相关	优点：可针对特定离子调控膜表面电荷，提升离子选择性，此外，离子与膜的结合对孔径有微调作用；缺点：对离子浓度与类型依赖较高	水处理、资源回收等

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