Abstract
Membrane nanofiltration provides a sustainable and energy-efficient platform for precise molecular separation. However, highly permselective and chemically stable membrane materials capable of operating under harsh conditions are currently lacking. Here we report a generalizable monomer–solvent dual engineering strategy that enables the one-step synthesis of chemically robust thiazole-linked polycrystalline covalent organic framework (COF) membranes via scalable interfacial polymerization under ambient conditions for ultraselective molecular separation. The fully π-conjugated aromatic skeleton and the spatially exposed heteroatoms on the irreversible thiazole linkages establish a lone-pair electron network, which not only forms an atomic hydration layer to protect the framework but also confers long-range regulation of electrostatic interactions. The thiazole-linked COF membranes exhibit remarkable structural stability in strong acids (e.g., 12 M HCl), good resistance to organic solvents and chlorine, and high pharmaceutical desalination permselectivity, achieving ion/pharmaceutical separation factors up to 690. This versatile thiazole-linked framework structure offers potential for the development of chemically stable aromatic conjugated COF membranes for diverse vital applications.
Similar content being viewed by others
Data availability
The all data generated in this study are provided in the Supplementary Information. Source data for the optimized structures of TbBa-azo and TbPa are present. Additional data are available from the corresponding author upon request. Source data are provided with this paper.
References
Meng, Q.-W. et al. Guanidinium-based covalent organic framework membrane for single-acid recovery. Sci. Adv. 9, eadh0207 (2023).
Wu, D. et al. Engineering bipolar covalent organic framework membranes for selective acid extraction. Angew. Chem. 137, e202503945 (2025).
Liu, X., Lin, W., Bader Al Mohawes, K. & Khashab, N. M. Ultrahigh proton selectivity by assembled cationic covalent organic framework nanosheets. Angew. Chem. Int. Ed. 64, e202419034 (2025).
Jian, M. et al. Artificial proton channel membrane with self-amplified selectivity for simultaneous waste acid recovery and power generation. ACS Nano 19, 16405–16414 (2025).
Hou, L. et al. Enabling highly selective acid recovery by 3D covalent organic frameworks membrane with sub-nanochannels. J. Membr. Sci. 731, 124242 (2025).
Zhou, L. et al. Covalent organic framework membrane with turing structures for deacidification of highly acidic solutions. Adv. Funct. Mater. 32, 2108178 (2022).
Lin, J. et al. Shielding effect enables fast ion transfer through nanoporous membrane for highly energy-efficient electrodialysis. Nat. Wat. 1, 725–735 (2023).
DuChanois, R. M. et al. Membrane materials for selective ion separations at the water–energy nexus. Adv. Mater. 33, 2101312 (2021).
Kim, J., Kim, J. F., Jiang, Z. & Livingston, A. G. Advancing membrane technology in organic liquids towards a sustainable future. Nat. Sustain. 8, 594–605 (2025).
Zhao, Y. et al. Enabling an ultraefficient lithium-selective construction through electric field–assisted ion control. Sci. Adv. 11, eadv6646 (2025).
Lee, T. H. et al. Microporous polyimine membranes for efficient separation of liquid hydrocarbon mixtures. Science 388, 839–844 (2025).
Côté, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).
Tan, K. T. et al. Covalent organic frameworks. Nat. Rev. Methods Primers 3, 1 (2023).
Zhou, Z. et al. Carbon dioxide capture from open air using covalent organic frameworks. Nature 635, 96–101 (2024).
Zhang, W. et al. Reconstructed covalent organic frameworks. Nature 604, 72–79 (2022).
Gruber, C. G. et al. Early stages of covalent organic framework formation imaged in operando. Nature 630, 872–877 (2024).
Bao, S. et al. Randomly oriented covalent organic framework membrane for selective Li+ sieving from other ions. Nat. Commun. 16, 3896 (2025).
Gao, X. & Ben, T. Chiral substrate-induced chiral covalent organic framework membranes for enantioselective separation of macromolecular drug. Nat. Commun. 16, 5210 (2025).
Tang, J. et al. Interface-confined catalytic synthesis of anisotropic covalent organic framework nanofilm for ultrafast molecular sieving. Adv. Sci. 12, 2415520 (2025).
Liu, J. et al. Self-standing and flexible covalent organic framework (COF) membranes for molecular separation. Sci. Adv. 6, eabb1110 (2020).
Wu, C. et al. Advanced covalent organic framework-based membranes for recovery of ionic resources. Small 19, 2206041 (2023).
Yang, H. et al. Solvent-responsive covalent organic framework membranes for precise and tunable molecular sieving. Sci. Adv. 10, eads0260 (2024).
Kang, C. et al. Interlayer shifting in two-dimensional covalent organic frameworks. J. Am. Chem. Soc. 142, 12995–13002 (2020).
Yuan, S. et al. Covalent organic frameworks for membrane separation. Chem. Soc. Rev. 48, 2665–2681 (2019).
Qian, C. et al. Imine and imine-derived linkages in two-dimensional covalent organic frameworks. Nat. Rev. Chem. 6, 881–898 (2022).
Cusin, L., Peng, H., Ciesielski, A. & Samorì, P. Chemical conversion and locking of the imine linkage: enhancing the functionality of covalent organic frameworks. Angew. Chem. 133, 14356–14370 (2021).
Meng, Q.-W. et al. Enhancing ion selectivity by tuning solvation abilities of covalent-organic-framework membranes. Proc. Natl. Acad. Sci. USA 121, e2316716121 (2024).
Lai, Z. et al. Covalent–organic-framework membrane with aligned dipole moieties for biomimetic regulable ion transport. Adv. Funct. Mater. 34, 2409356 (2024).
Meng, Q.-W. et al. Optimizing selectivity via membrane molecular packing manipulation for simultaneous cation and anion screening. Sci. Adv. 10, eado8658 (2024).
Zheng, S. et al. Quantitative skeletal-charge engineering of anion-selective COF membrane for ultrahigh osmotic power output. J. Am. Chem. Soc. 147, 15777–15786 (2025).
Wu, T. et al. Imine-linked 3D covalent organic framework membrane featuring highly charged sub-1 nm channels for exceptional lithium-ion sieving. Adv. Mater. 37, 2415509 (2025).
Li, S. et al. Synthesis of single-crystalline sp2-carbon-linked covalent organic frameworks through imine-to-olefin transformation. Nat. Chem. 17, 226–232 (2025).
Liu, C.-H. & Perepichka, D. F. Bilayer covalent organic frameworks take a twist. Nat. Chem. 17, 471–472 (2025).
Liu, R. et al. Harvesting singlet and triplet excitation energies in covalent organic frameworks for highly efficient photocatalysis. Nat. Mater. 24, 1245–1257 (2025).
Yan, R. et al. A thiazole-linked covalent organic framework for lithium-sulphur batteries. Angew. Chem. Int. Ed. 62, e202302276 (2023).
Zhao, Y. et al. Robust thiazole-linked covalent organic frameworks with post-modified azobenzene groups: photo-regulated dye adsorption and separation. Adv. Funct. Mater. 34, 2401895 (2024).
Hou, Y. et al. Rigid covalent organic frameworks with thiazole linkage to boost oxygen activation for photocatalytic water purification. Nat. Commun. 15, 7350 (2024).
Liu, H. et al. Metal-incorporated covalent organic framework membranes via layer-by-layer self-assembly for efficient antibiotic desalination. Desalination 600, 118537 (2025).
Zhou, L. et al. Ultrathin cyclodextrin-based nanofiltration membrane with tunable microporosity for antibiotic desalination. J. Membr. Sci. 715, 123504 (2025).
Bai, Y. et al. Microstructure optimization of bioderived polyester nanofilms for antibiotic desalination via nanofiltration. Sci. Adv. 9, eadg6134 (2023).
Guo, Q. et al. Enhancing the interfacial interactions in PVDF/COF composite nanofiltration membranes for efficient antibiotic separation. Composites Communications 58, 102507 (2025).
Abraham, M. J. et al. GROMACS: high performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX 1-2, 19–25 (2015).
Kühne, T. D. et al. CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations. J. Chem. Phys. 152, 194103 (2020).
Neese, F. Software update: the ORCA program system, version 4.0. WIREs Comput. Mol. Sci. 8, e1327 (2018).
Neese, F. Software update: the ORCA program system—Version 5.0. WIREs Comput. Mol. Sci. 12, e1606 (2022).
Lu, T. & Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).
Lu, T. A comprehensive electron wavefunction analysis toolbox for chemists. Multiwfn. J. Chem. Phys. 161, 082503 (2024).
Jusélius, J., Sundholm, D. & Gauss, J. Calculation of current densities using gauge-including atomic orbitals. J. Chem. Phys. 121, 3952–3963 (2004).
Fliegl, H., Taubert, S., Lehtonen, O. & Sundholm, D. The gauge including magnetically induced current method. Phys. Chem. Chem. Phys. 13, 20500–20518 (2011).
Willems, T. F. et al. Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials. Microporous and Mesoporous Materials 149, 134–141 (2012).
Bannwarth, C. et al. Extended tight-binding quantum chemistry methods. WIREs Comput. Mol. Sci. 11, e1493 (2021).
Acknowledgements
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (Grant No. 22576109 to G.H.), the Tianjin Applied Basic Research Diversified Investment–Urban Fire Protection Project (Grant No. 24JCQNJC00010 to G.H.), the Tianjin Natural Science Foundation Project (Grant No. 24JCYBJC01550 to G.H.), and the Fundamental Research Funds for the Central Universities (040-63253198 to G.H.). Special thanks are also made to other members of the Han Gang Research Lab for their helpful suggestions related to materials characterization.
Author information
Authors and Affiliations
Contributions
G.H. proposed and supervised the project. Y.L. and S.F. designed and conducted the experiments and analyzed the experimental results. Y.L., J.T., and M.T. participated in the membrane structural characterization. Y.L. and S.F. conducted the molecular simulations. Y.L., S.F., F.Z., Z.P., J.Z., and G.H. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature Communications thanks Teng Ben, Qi Sun and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. A peer review file is available.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Source data
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.
About this article
Cite this article
Liao, Y., Fang, S., Tang, J. et al. Thiazole-conjugated covalent organic framework membranes enable ultraselective molecular desalination under strongly acidic conditions. Nat Commun (2026). https://doi.org/10.1038/s41467-025-68171-9
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41467-025-68171-9
