Precise molecular sieving in polycrystalline covalent organic framework membranes
7 affiliations
- 1Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117585, Singapore.
- 2Key Lab of Functional Polymers for Sustainability of Jiangsu, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, P. R. China.
- 3Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis Way, Innovis #08-03, Singapore 138634, Singapore.
- 4College of Safety Science and Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, P. R. China.
- 5Centre for Hydrogen Innovations, National University of Singapore, 1 Engineering Drive 3, Singapore 117580, Singapore.
- 6National University of Singapore (Suzhou) Research Institute, Suzhou 215123, Jiangsu, P. R. China.
- 7National University of Singapore (Chongqing) Research Institute, Chongqing 401120, P. R. China.
Abstract
Covalent organic frameworks (COFs) unlock opportunities to unite rapid mass transport with molecular-level sieving through membranes. However, achieving long-range crystallographic order within these membranes remains a central challenge that limits their separation precision. Here, we report a monomer-driven strategy for the ambient-condition fabrication of COF polycrystalline membranes featuring definite lattice order and polyhedral textures, reminiscent of benchmark metal-organic framework counterparts. Using a rigid, π-conjugated pyrene-centered tetraamine, we enable nonepitaxial intergrowth of faceted COF crystals on a porous support, yielding a 350-nanometer-thick membrane with a record-high Brunauer-Emmett-Teller surface area of 2121 square meters per gram among COF separation membranes of comparable pore size. The resulting COF membrane preserves its crystallographic order and polyhedral texture even after 1 month of solvent exposure while uniquely combining increased surface stiffness with high tensile ductility. Notably, we demonstrate its superior liquid-phase molecular selectivity, outperforming COF analogs with considerably smaller pore apertures, and elucidate an unambiguous correlation between crystallographic order and permselectivity. This work positions crystallographic ordering as a guiding principle for COF membranes, opening more possibilities at the intersection of framework materials and separation technologies.
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BibTeX
@article{shi2026precise,
title = {{Precise molecular sieving in polycrystalline covalent organic framework membranes}},
author = {Xiansong Shi and Haipei Shao and Xin Zhang and Fen Huang and Qixing Liu and He Li and Wei Zhao and Junyu Ren and Yunchuan Pu and Wen-Hua Li and Nengxiu Zhu and Ming Lin and Dan Zhao},
journal = {Science Advances},
year = {2026},
month = oct,
doi = {10.1126/sciadv.aee9683},
url = {https://www.science.org/doi/10.1126/sciadv.aee9683},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Precise molecular sieving in polycrystalline covalent organic framework membranes
AU - Xiansong Shi
AU - Haipei Shao
AU - Xin Zhang
AU - Fen Huang
AU - Qixing Liu
AU - He Li
AU - Wei Zhao
AU - Junyu Ren
AU - Yunchuan Pu
AU - Wen-Hua Li
AU - Nengxiu Zhu
AU - Ming Lin
AU - Dan Zhao
PY - 2026
DA - 2026/10/02
JO - Science Advances
DO - 10.1126/sciadv.aee9683
UR - https://www.science.org/doi/10.1126/sciadv.aee9683
AB - Covalent organic frameworks (COFs) unlock opportunities to unite rapid mass transport with molecular-level sieving through membranes. However, achieving long-range crystallographic order within these membranes remains a central challenge that limits their separation precision. Here, we report a monomer-driven strategy for the ambient-condition fabrication of COF polycrystalline membranes featuring definite lattice order and polyhedral textures, reminiscent of benchmark metal-organic framework counterparts. Using a rigid, π-conjugated pyrene-centered tetraamine, we enable nonepitaxial intergrowth of faceted COF crystals on a porous support, yielding a 350-nanometer-thick membrane with a record-high Brunauer-Emmett-Teller surface area of 2121 square meters per gram among COF separation membranes of comparable pore size. The resulting COF membrane preserves its crystallographic order and polyhedral texture even after 1 month of solvent exposure while uniquely combining increased surface stiffness with high tensile ductility. Notably, we demonstrate its superior liquid-phase molecular selectivity, outperforming COF analogs with considerably smaller pore apertures, and elucidate an unambiguous correlation between crystallographic order and permselectivity. This work positions crystallographic ordering as a guiding principle for COF membranes, opening more possibilities at the intersection of framework materials and separation technologies.
SN - 2375-2548
ER -