Position：Home >> Abstract

Recent progress in interfacial polymerization of COF membranes and their formation mechanisms
Authors： LUO Wei1， HUANG Siyu1， LI Weiyi2， MENG Mianwu1， LIU Jie1， JIANG Liping1
Units： 1. School of Environment and Resources，Guangxi Normal University，Guilin 541006，China; 2. School of Chemistry and Pharmaceutical Science, Guangxi Normal University, Guilin 541004, China
KeyWords： COF membranes; interfacial polymerization; membrane-formation mechanism; liquid-liquid interfacial polymerization
ClassificationCode：TQ028
year,volume(issue):pagination： 2026,46(1):199-218

Abstract：
 In recent years, covalent organic framework (COF) membranes prepared by interfacial polymerization have been widely applied to organic solvent nanofiltration, molecular sieving and other separation processes. Elucidating the formation mechanisms and kinetics is crucial for tailoring the microstructures and optimizing the separation performance. This review summarizes recent progress in COF membranes from two aspects: liquid-liquid interfacial polymerization strategies and the underlying membrane-formation mechanisms. Particular emphasis is on how the monomer configuration, solvent systems, interfacial activation strategies and interfacial tension regulation affect the structure and performance of COF membranes, with the aim of clarifying the formation pathways of COF membranes prepared at liquid-liquid interfaces. This review is concluded by discussing the current bottlenecks in mechanistic studies and proposing future research directions to guide the rational design and optimization of COF membranes and to broaden their application scope.
 

Funds：
国家自然科学基金项目（22468015, 22466009）； 广西自然科学基金项目（2024GXNSFAA010134）； 广西科技计划项目-广西科技基地和人才专项(桂AD25069041)； 广西研究生教育创新计划项目（YCSW2025176）

AuthorIntro：
罗伟（1996-），安徽宿州人，硕士研究生，研究方向为COF膜的制备及水环境中碘离子的捕获

Reference：
[1]Eke J, Yusuf A, Giwa A, et al. The global status of desalination: An assessment of current desalination technologies, plants and capacity[J]. Desalination, 2020, 495: 114633-114650.
[2]Asif M B, Zhang Z H. Ceramic membrane technology for water and wastewater treatment: A critical review of performance, full-scale applications, membrane fouling and prospects[J]. Chem Eng J, 2021, 418: 129481-129499.
[3]Sarkar P, Modak S, Ray S, et al. Fast water transport through sub-5 nm polyamide nanofilms: The new upper-bound of the permeance-selectivity trade-off in nanofiltration[J]. J Mater Chem A, 2021, 9(36): 20714-20724.
[4]Chen L F, Zhang B Y, Chen L L, et al. Hydrogen-bonded organic frameworks: Design, applications, and prospects[J]. Mater Adv, 2022, 3(9): 3680-3708.
[5]Song Y P, Sun Q, Aguila B, et al. Opportunities of covalent organic frameworks for advanced applications[J]. Adv Sci, 2019, 6(2): 1801410-1801444.
[6]Cté A P, Benin A I, Ockwig N W, et al. Porous, crystalline, covalent organic frameworks[J]. Science, 2005, 310(5751): 1166-1170.
[7]Huang T H, Zhang W F, Yang S, et al. Imine-linked covalent organic frameworks: Recent advances in design, synthesis, and application[J]. SmartMat, 2024, 5(6): e1309.
[8]Wang R, Ding L, Xue J, et al. Green and large-scale production of covalent organic framework nanofiltration membranes[J]. Commun Mater, 2025, 6(1): 61.
[9]Dey K, Pal M, Rout K C, et al. Selective molecular separation by interfacially crystallized covalent organic framework thin films[J]. J Am Chem Soc, 2017, 139(37): 13083-13091.
[10]Burke D W, Jiang Z W, Livingston A G, et al. 2D covalent organic framework membranes for liquid-phase molecular separations: state of the field, common pitfalls, and future opportunities[J]. Adv Mater, 2024, 36(1): 2300525.
[11]Xu T, Cao L, An S H, et al. A homochiral covalent organic framework membrane for the enantioseparation and fractionation of amino acids[J]. Nat Commun, 2025, 16(1): 7803.
[12]Fang L, Xu H, Qiu S Y, et al. Autocatalytic interfacial synthesis of self-standing amide-linked covalent organic framework membranes[J]. Angew Chem Int Edit, 2025, 64(13): e202423220.
[13]Chen M Y, Yang K, Wang J, et al. In situ growth of imine-bridged anion-selective COF/AAO membrane for ion current rectification and nanofluidic osmotic energy conversion[J]. Adv Funct Mater, 2023, 33(36): 2302427.
[14]Wang J, Zhang J W, Jin P R, et al. A covalent organic framework membrane with highly selective and permeable artificial sodium channels via ion recognition[J]. Nat Commun, 2025, 16(1): 7346.
[15]Yang F, Guo J, Han C Z, et al. Turing covalent organic framework membranes via heterogeneous nucleation synthesis for organic solvent nanofiltration[J]. Sci Adv, 2024, 10(50): eadr9260.
[16]Liu H H, Tian F, Lei L, et al. Metal-incorporated covalent organic framework membranes via layer-by-layer self-assembly for efficient antibiotic desalination[J]. Desalination, 2025, 600: 118537.
[17]Dai B L, Hu Y J, Ding Y D, et al. Innovative construction of nano-wrinkled polyamide membranes using covalent organic framework nanoflowers for efficient desalination and antibiotic removal[J]. Desalination, 2024, 570: 117083.
[18]Guo Z Y, Li W P, Wu H, et al. Reverse filling approach to mixed matrix covalent organic framework membranes for gas separation[J]. Nat Commun, 2025, 16(1): 3617.
[19]Zhang J C, Sun X, Xin J H, et al. Facile preparation of mixed-matrix membrane for highly selective separation of CO2 via a defected Zr-MOF fluorination-modified strategy[J]. Acs Sustain Chem Eng, 2025, 13(6): 2368-2379.
[20]Hoque B, Khan M Y, Hanif A, et al. Tailored design of CO2-selective mixed-matrix membranes using nitrile-functionalized COFs as 2D nanofillers[J]. J Environ Chem Eng, 2024, 12(3): 112695.
[21]Kim S M, Hong S, Duy Nguyen B T, et al. Effect of additives during interfacial polymerization reaction for fabrication of organic solvent nanofiltration (OSN) membranes[J]. Polymers, 2021, 13(11): 1716.
[22]Liu F, Wang L L, Li D W, et al. A review: the effect of the microporous support during interfacial polymerization on the morphology and performances of a thin film composite membrane for liquid purification[J]. RSC Adv, 2019, 9(61): 35417-35428.
[23]Meng W J, Li Y, Zhao Z Q, et al. Ultrathin 2D covalent organic framework film fabricated via langmuir-blodgett method with a “two-in-one” type monomer[J]. Chem Res Chinese U, 2022, 38(2): 440-445.
[24]Zhang Z M, Yang H, Cao C L, et al. Vapor-liquid interfacial polymerization of covalent organic framework membranes for efficient alcohol dehydration[J]. J Membr Sci, 2022, 641: 119905.
[25]Khan N A, Zhang R N, Wu H, et al. Solid-vapor interface engineered covalent organic framework membranes for molecular separation[J]. J Am Chem Soc, 2020, 142(31): 13450-13458.
[26]Siow W J S, Chong J Y, Ong J H, et al. Vapor/vapor-solid interfacial growth of covalent organic framework membranes on alumina hollow fiber for advanced molecular separation[J]. Angew Chem Int Edit, 2024, 63(32): e202406830.
[27]Hong J X, Liu M H, Liu Y X, et al. Solid-liquid interfacial engineered large-area two-dimensional covalent organic framework films[J]. Angew Chem Int Edit, 2024, 63(9): e202317876.
[28]Wang R, Shi X S, Zhang Z, et al. Unidirectional diffusion synthesis of covalent organic frameworks (COFs) on polymeric substrates for dye separation[J]. J Membr Sci, 2019, 586: 274-280.
[29]蒋成浩,冯霄,王博. 共价有机框架膜的制备及其在海水淡化和水处理领域的研究进展[J]. 化学学报, 2020, 78(6): 466.
[30]Yue L P, Kong F X, Wang Y, et al. Evolution of morphology, structure, and performance of the COF membranes with monomer concentrations: Enabling effective desalination and kinetics analysis[J]. Desalination, 2024, 583: 117712.
[31]Shevate R, Shaffer D L. Large-area 2D covalent organic framework membranes with tunable single-digit nanopores for predictable mass transport[J]. ACS Nano, 2022, 16(2): 2407-2418.
[32]Ding C H, Du Y Y, Fischer T, et al. Liquid-liquid-solid interfacial polymerization approach to rapid fabrication of large-sized, self-standing structured COF membranes[J]. J Mater Chem A, 2025.
[33]Li Y Q, Zhang Q Q, Dai Z D, et al. Surfactant-assisted construction of covalent organic frameworks[J]. Adv Sci, 2025, 12(20): 2501580.
[34]Gao S Q, Li Z Y, Yang Y Y, et al. The ionic liquid-H2O interface: A new platform for the synthesis of highly crystalline and molecular sieving covalent organic framework membranes[J]. ACS Appl Mater Inter, 2021, 13(30): 36507-36516.
[35]Wang R, Shi X S, Xiao A K, et al. Interfacial polymerization of covalent organic frameworks (COFs) on polymeric substrates for molecular separations[J]. J Membr Sci, 2018, 566: 197-204.
[36]Vitaku E, Dichtel W R. Synthesis of 2D imine-linked covalent organic frameworks through formal transimination reactions[J]. J Am Chem Soc, 2017, 139(37): 12911-12914.
[37]Matsumoto M, Valentino L, Stiehl G M, et al. Lewis-acid-catalyzed interfacial polymerization of covalent organic framework films[J]. Chem, 2018, 4(2): 308-317.
[38]Li Y, Wu Q X, Guo X H, et al. Laminated self-standing covalent organic framework membrane with uniformly distributed subnanopores for ionic and molecular sieving[J]. Nat Commun, 2020, 11(1): 599.
[39]Liu J T, Han G, Zhao D L, et al. Self-standing and flexible covalent organic framework (COF) membranes for molecular separation[J]. Sci Adv, 2020, 6(41): eabb1110.
[40]Sun Q, Song Z, Du J C, et al. Covalent organic framework membranes with regulated orientation for monovalent cation sieving[J]. ACS Nano, 2024, 18(39): 27065-27076.
[41]Wang X Y, Shi B B, Yang H, et al. Assembling covalent organic framework membranes with superior ion exchange capacity[J]. Nat Commun, 2022, 13(1): 1020.
[42]Du J C, Sun Q, He W, et al. A 2D soft covalent organic framework membrane prepared via a molecular bridge[J]. Adv Mater, 2023, 35(26): 2300975.
[43]Du J C, Yao A, Sun Q, et al. Ultrafast interfacial self-assembly toward bioderived polyester COF membranes with microstructure optimization[J]. Adv Mater, 2024, 36(32): 2405744.
[44]Wang M D, Wang Y T, Zhao J Y, et al. Electrochemical interfacial polymerization toward ultrathin COF membranes for brine desalination[J]. Angew Chem Int Edit, 2023, 62(13): e202219084.
[45]Wang H, He B, Liu F, et al. Orientation transitions during the growth of imine covalent organic framework thin films[J]. J Mater Chem C, 2017, 5(21): 5090-5095.  
[46]Wu Y L, Wang Y X, Xu F, et al. Solvent-induced interfacial polymerization enables highly crystalline covalent organic framework membranes[J]. J Membr Sci, 2022, 659: 120799. 
[47]Wu D C, Gu N, Yao J R, et al. Recent advances in room-temperature synthesis of covalent organic frameworks[J]. Chem Sci, 2025.  
[48]Yang H, Zhang H Y, Kang C J, et al. Solvent-responsive covalent organic framework membranes for precise and tunable molecular sieving[J]. Sci Adv, 2024, 10(51): eads0260.
[49]Wang H J, Zhao J S, Li Y, et al. Aqueous two-phase interfacial assembly of COF membranes for water desalination[J]. Nano-Micro Lett, 2022, 14(1): 216.
[50]Chen J J, Li R L, Liu S Y, et al. Surfactant-assisted interfacial polymerization towards high-crystallinity COF membranes for organic solvent nanofiltration[J]. J Membr Sci, 2024, 694: 122404.
[51]Khan N A, Zhang R N, Wang X Y, et al. Assembling covalent organic framework membranes via phase switching for ultrafast molecular transport[J]. Nat Commun, 2022, 13(1): 3169.
[52]Liu K, Yin C C, Gao J L, et al. Temperature-swing synthesis of highly crystalline covalent organic framework films for fast and precise molecular separations[J]. Angew Chem Int Edit, 2025, 64(12): e202422333.
[53]Ye X Y, Liu R Y, Mu X Y, et al. Superacid in situ protected synthesis of covalent organic frameworks[J]. J Am Chem Soc, 2025, 147(8): 6942-6957.  
[54]Zhu T H, Kong Y, Lyu B, et al. 3D covalent organic framework membrane with fast and selective ion transport[J]. Nat Commun, 2023, 14(1): 5926.
[55]Hu X F, Jiang T, Fan H Q, et al. Dual-regulated covalent organic framework membranes with near-theoretical pore sizes for angstrom-scale ion separations[J]. Sci Adv, 2025, 11(46): eady3587.
[56]Zhao B, Luo C Q, Feng Y W, et al. A pH-responsive covalent organic framework membrane based on flexible building blocks for superhigh-flux dye/salt separation[J]. Desalination, 2025, 606: 118783.
[57]Du J C, Guan J,AL-Thuraya A A, et al. Asymmetric ionic covalent organic framework membranes with tunable Turing patterns prepared via ion regulated strategy[J]. Nat Commun, 2025, 16(1): 1-17.
[58]Du J C, Sun Q, Cao D, et al. Turing COF membranes with tunable patterns for antibiotic desalination[J]. JACS Au, 2025, 5(10): 5048-5058.
[59]Khalil S, Sun M H, Yang Z, et al. In situ observation of covalent organic framework growth in solution[J]. Small, 2025, 21(39): e02087.
[60]Gruber C G, Frey L, Guntermann R, et al. Early stages of covalent organic framework formation imaged in operando[J]. Nature,2024, 630:872-877.
[61]Wang L, Wang X, Zhao Z L,et al. Stranski-krastanov growth of two-dimensional covalent organic framework films[J].J Am Chem Soc, 2024 ,146 (20):14079-14085.
[62]Daliran S, Oveisi A R, Dhakshinamoorthy A, et al. Probing defects in covalent organic frameworks[J]. ACS Appl Mater Inter, 2024, 16(38): 50096-50114.
[63]Wang R Y, Yang T X, Zhang H S, et al. Unveiling the interfacial polymerization for COF membranes: Real-time monitoring of flow instability and film growth[J]. AIChE J, 2026, 72(2): e70120.
[64]Sun X X, Wang B, Zhou P L, et al. Novel polyamide forward osmosis membrane prepared via synergistically substrate-floating interfacial polymerization and salt regulation for efficient solvent recovery[J]. J Membr Sci, 2023, 678: 121657.
[65]Zhuang H F, Guo C, Huang J L, et al. Hydrazone-linked covalent organic frameworks[J]. Angew Chem Int Edit, 2024, 136(31): e202404941.
[66]Zhao M Y, Luo X Z, Li D, et al. Monitoring the Interfacial polymerization and membrane fouling of selective layer with boronate ester linkages via aggregation-induced emission[J]. Chinese J Polym Sci, 2025: 1-11.
[67]Xu Y, Tian B D, Zhang R K, et al. An acylhydrazone-linked covalent organic framework for removal of Cu(Ⅱ) from aqueous solution and its applications in catalysis[J]. Micropor Mesopor Mat, 2024, 366: 112959.
[68]Niu C P, Zhang C R, Liu X, et al. Synthesis of propenone-linked covalent organic frameworks via Claisen-Schmidt reaction for photocatalytic removal of uranium[J]. Nat Commun, 2023, 14(1): 4420.
[69]Fercher A F. Optical coherence tomography - development, principles, applications [J]. Z Med Phys, 2010, 20(4): 251-276.
[70]刘杰,程良红,徐期勇,等. 应用光学相干断层成像技术探索膜蒸馏过程的研究进展[J]. 膜科学与技术，2024, 44(1)：179-187.
[71]Cleeton C, Sarkisov L. Inverse design of metal-organic frameworks using deep dreaming approaches[J]. Nat Commun, 2025, 16(1): 4806.
[72]Rong Z C, Chen Z H, Luong F, et al. Algorithmic iterative reticular synthesis of zeolitic imidazolate framework crystals[J]. Nat Synth, 2025: 1-11.
 

Service：
【Download】【Collect】

《膜科学与技术》编辑部 Address: Bluestar building, 19 east beisanhuan road, chaoyang district, Beijing; 100029 Postal code; Telephone：010-80492417/010-80485372; Fax：010-80485372 ; Email：mkxyjs@163.com

京公网安备11011302000819号