Covalent Organic Framework Membranes for Selective Ion Separation

Hao Zhang; Fangyuan Xu; Zhimin Lin

doi:10.62051/ijmsts.v5n1.05

Authors

Hao Zhang
Fangyuan Xu
Zhimin Lin

DOI:

https://doi.org/10.62051/ijmsts.v5n1.05

Keywords:

Covalent organic frameworks, Membranes, Ion separation, Desalination, Lithium extraction

Abstract

The escalating global urgency for clean water and critical mineral recovery necessitates separation technologies that transcend the inherent permeability-selectivity trade-offs of conventional polymeric membranes. Covalent Organic Frameworks (COFs), distinguished by their precise reticular chemistry, tunable pore architectures, and modular functionality, have emerged as a transformative platform for next-generation ion separation. This review systematically evaluates recent breakthroughs in the engineering of COF-based membranes, focusing on the nexus between fabrication strategies and application performance. We critically examine diverse synthesis methodologies, including interfacial polymerization, in situ growth, and electrophoretic deposition, highlighting how these techniques control membrane crystallization and defect minimization. Furthermore, the review details the deployment of these materials across three pivotal sectors: seawater desalination, where they achieve superior salt rejection; lithium resource extraction, enabling high-precision Li⁺/Mg²⁺ differentiation; and the purification of drinking water from heavy metals and radionuclides. The discussion concludes by identifying the critical bottlenecks in scalability and long-term stability that must be addressed to transition COF membranes from laboratory prototypes to industrial implementation.

References

[1] Kingsbury Ryan. "A guide to ion separations for the global energy transition", Joule, 9, 102134, 2025.

[2] Asif Muhammad Bilal, Zhang Zhenghua. "Ceramic membrane technology for water and wastewater treatment: A critical review of performance, full-scale applications, membrane fouling and prospects", Chemical Engineering Journal, 418, 129481, 2021.

[3] Tao Yueheng, Cui Yujie, Wang Houxiang, Li Zhaolei, Qian Zhangjiashuo, Zhang Peipei, Zhou Hongjian, Shi Minjie. "High-Efficiency Electrochemical Desalination: The Role of a Rigid Pseudocapacitive Polymer Electrode with Diverse Active Sites", Advanced Functional Materials, 35, 2414805, 2025.

[4] He Nan, Yang Yongfang, Wang Haonan, Li Fan, Jiang Bo, Tang Dawei, Li Lin. "Ion-Transfer Engineering via Janus Hydrogels Enables Ultrahigh Performance and Salt-Resistant Solar Desalination", Advanced Materials, 35, 2300189, 2023.

[5] Bi Songshan, Wang Huimin, Wang Rui, Yang Min, Tian Jinlei, Chen Jun, Niu Zhiqiang. "Simultaneous Heavy-Metal Ion Adsorption and Electricity Generation From Wastewater via “Heavy-Metal Removal Batteries”", Advanced Materials, 37, 2503776, 2025.

[6] Li Lei, Liu Ziyi, Xu Xiaocheng, Xu Lei, Yang Xiaofan, Guan Hanxi, Li Zhonglong, Xiao Chengliang. "A negatively-charged supramolecular trap for precisely catching strontium ion", Nature Communications, 16, 2606, 2025.

[7] Wang Deqi, Zhang Ting, Min Fan, Gao Yifeng, Zhu Jiaming, Xie Ganhua, Chu Zonglin. "Superwettable-Membrane-Assisted Extraction and Separation as a General Method for Removal of Organic Pollutants From Water", Advanced Science, n/a, e15526, 2025.

[8] Xu Shu, Feng Zimou, Bao Linyun, Zhu Zhiyang, Wu Shenyang, Yang Yi, Lu Xinglin. "Biocatalytic nanomotor-assisted ultrafiltration membrane system for selective removal and transformation of phenolic contaminants", Matter, 8, 2025.

[9] Zhang Qing Yun, Zhang Lin Juan, Zhu Jian Qiu, Gong Le Le, Huang Zhe Cheng, Gao Feng, Wang Jian Qiang, Xie Xian Qing, Luo Feng. "Ultra-selective uranium separation by in-situ formation of π-f conjugated 2D uranium-organic framework", Nature Communications, 15, 453, 2024.

[10] Zhao Shilei, Feng Tiantian, Zhang Jiacheng, Cao Meng, Feng Lijuan, Ma Yue, Liu Tao, Yuan Yihui, Wang Ning. "Coordination-Induced Magnetism Strategy for Highly Selective and Efficient Uranium Separation", Advanced Science, 11, 2408642, 2024.

[11] Li Nan, Wang Zhi, Wang Jixiao. "Biomimetic hydroxypropyl-β-cyclodextrin (Hβ-CD) / polyamide (PA) membranes for CO2 separation", Journal of Membrane Science, 668, 121211, 2023.

[12] Wang Qingyi, Dong Yongping, Ma Junmei, Wang Huimin, Xue Xuping, Bai Chaojie, Lin Mingjie, Luo Lingping, Gao Congjie, Xue Lixin. "Polyamide/polyethylene thin film composite (PA/PE-TFC) NF membranes prepared from reverse-phase interface polymerization (RIP) for improved Mg(II)/Li(I) separation", Desalination, 553, 116463, 2023.

[13] Xiao Minhao, Wang Xinyi, Kim Sungsoon, Wu Jishan, Quezada-Renteria J. Alan, Abdelrahman Mohamed, Jassby David, Hoek Eric M. V. "Nanobubbles as pore-forming agents in non-solvent induced phase separation of polysulfone ultrafiltration membranes", Chemical Engineering Journal, 521, 166802, 2025.

[14] Xu Le, Jiang Peng, Peng Lu, Cai Chaochen, Lu Yongji, Zhu Zhenyu, Wang Hongxia, Wei Xin, Lin Tong. "Polyvinylidene fluoride/polysulfone nanofiber membranes with dual high-efficiency and self-regenerating filtration for solid-oil aerosols", Chemical Engineering Journal, 524, 168925, 2025.

[15] Li Z., Yang Y. W. "Macrocycle-Based Porous Organic Polymers for Separation, Sensing, and Catalysis", Advanced materials (Deerfield Beach, Fla), 34, e2107401, 2022.

[16] Jin Yuan-Hang, Li Meng-Hao, Yang Ying-Wei. "Covalent Organic Frameworks for Membrane Separation", Advanced Science, 12, 2412600, 2025.

[17] Ebrahimi Arash, Krivosudský Lukáš, Khodabakhshi Saeed, Khaleghiabbasabadi Masoud, Sadeghi Masoud, Motola Martin. "Polyoxometalate-based covalent organic frameworks: The next generation of heterogeneous catalysts", Coordination Chemistry Reviews, 548, 217201, 2026.

[18] Côté Adrien P., Benin Annabelle I., Ockwig Nathan W., O'Keeffe Michael, Matzger Adam J., Yaghi Omar M. "Porous, Crystalline, Covalent Organic Frameworks", Science, 310, 1166-1170, 2005.

[19] Shao Mingchao, Chen Jinyang, Gao Wenqiang, Zhang Qingsong, Wei Xiaofang, Kuang Junhua, Liu Guocai, Sun Yang, Bian Yangshuang, Wang Chengyu, Qin Mingcong, Yang Xueli, Dong Jichen, Liu Yunqi, Guo Yunlong. "Reversible shape memory two-dimensional covalent organic frameworks", Nature Communications, 16, 9025, 2025.

[20] Zhang Mingshi, Chen Yao, Zhang Zhenjie. "Single-crystalline covalent organic frameworks: Synthesis, characterizations, and functions", Coordination Chemistry Reviews, 546, 217075, 2026.

[21] Weng Jia-Yong, Yue Ming, Li Qi, Yang Yiwen, Wang Yi-Rong, Chen Yifa, Li Shun-Li, Lan Ya-Qian. "3D interpenetrated covalent organic frameworks", Coordination Chemistry Reviews, 535, 216614, 2025.

[22] Ye Xingyao, Liu Ruoyang, Mu Xinyu, Tao Shanshan, Yang Hao, Gao Xuejiao J., Yang Shuo-Wang, Jiang Donglin. "Superacid In Situ Protected Synthesis of Covalent Organic Frameworks", Journal of the American Chemical Society, 147, 6942-6957, 2025.

[23] Li Jingkun, Wan Yuqi, Luo Zhixuan, Yang Chunming, Ozaki Yukihiro, Yan Xiuping, Wang Jian-Gan, Pi Fuwei. "Azine-Pyridine Frame Generated Covalent Organic Frameworks and Self-Polymerized Films", Angewandte Chemie International Edition, 64, e202509221, 2025.

[24] Ding San-Yuan, Wang Wei. "Covalent organic frameworks (COFs): from design to applications", Chemical Society Reviews, 42, 548-568, 2013.

[25] Colson John W., Dichtel William R. "Rationally synthesized two-dimensional polymers", Nature Chemistry, 5, 453-465, 2013.