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Scalable and Versatile Fabrication of Free-Standing Covalent Organic Framework Membranes with Tunable Microstructure for Molecular Separation
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Nanotechnology and Functional Materials. Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering. (Nanotechnology and Functional Materials)
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.ORCID iD: 0000-0002-1587-8073
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Nanotechnology and Functional Materials.ORCID iD: 0000-0002-5496-9664
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2025 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 147, no 32, p. 29271-29281Article in journal (Refereed) Published
Abstract [en]

Covalent organic framework (COF) membranes hold significant promise for applications in separation, catalysis, and energy conversion; however, their industrial adoption has been hindered by the lack of scalable and efficient fabrication methods. Here, we present a fast, versatile, and broadly applicable strategy for fabricating free-standing and flexible COF membranes by casting precursor suspensions, followed by heat treatment under controlled humidity. This approach enables the fabrication of COF membranes with lateral dimensions up to several square decimeters and thicknesses that are tunable down to submicron levels within 1 h. It demonstrates remarkable versatility for producing a family of ketoenamine-linked COF membranes through the condensation of 1,3,5-triformylphloroglucinol with various amine monomers differing in length, side groups, and geometry. The resulting crack-free COF membranes exhibit high mechanical strength, with ultimate tensile strength up to 60 MPa and Young’s modulus up to 1.7 GPa, as well as exceptionally high porosity, with Brunauer–Emmett–Teller (BET) surface areas reaching up to 2226 m2 g–1. More importantly, the morphology, porosity, and crystallinity of the membranes can be finely tuned by modulating the heating conditions. The membranes with optimized microstructures demonstrate excellent separation performance, achieving over 99% rejection in nanofiltration of aqueous dye solutions, and a separation factor of 11 with an H2 permeance of 2857 GPU in H2/CO2 gas separation. This approach provides a scalable and effective pathway toward large-scale COF membrane manufacturing for advanced molecular separations and other membrane-based technologies.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2025. Vol. 147, no 32, p. 29271-29281
National Category
Nanotechnology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
URN: urn:nbn:se:uu:diva-565436DOI: 10.1021/jacs.5c08788ISI: 001540510200001PubMedID: 40735926Scopus ID: 2-s2.0-105013578719OAI: oai:DiVA.org:uu-565436DiVA, id: diva2:1990765
Available from: 2025-08-21 Created: 2025-08-21 Last updated: 2025-10-22Bibliographically approved
In thesis
1. Scalable Fabrication of Structured Covalent Organic Frameworks for Chemical Separation
Open this publication in new window or tab >>Scalable Fabrication of Structured Covalent Organic Frameworks for Chemical Separation
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

 Large-scale chemical separations underpin modern industry yet consume 10–15% of global energy, driving the need to replace thermal operations with membrane- and sorbent-based alternatives of higher efficiency. This thesis advances covalent organic frameworks (COFs) toward practical deployment by focusing on scalable fabrication and processing routes that preserve performance while enabling industrial integration. The intrinsic advantages of COFs—uniform porosity, tunability, and stability—are outlined alongside application-driven requirements for separation materials and processes. For membranes, this entails ultrathin, defect-free active layers on robust supports compatible with continuous manufacturing; for sorbents, it requires short diffusion pathways, macroscopic structure, and low-cost, high-throughput fabrication. A critical survey of fabrication strategies identifies nanosheet assembly and support-infusion liquid–liquid interfacial polymerization as promising continuous routes for COF membranes, while highlighting time and footprint reduction as key issues for structured COF sorbent fabrication. Two novel, scalable fabrication strategies are introduced: (i) a precursor-casting method yielding continuous sub-micron β-ketoenamine COF films, adapted to manufacture thin-film composite membranes on polymeric substrates; and (ii) a gel-based approach for imine and β-ketoenamine COFs, producing hierarchically porous sorbents with rapid adsorption kinetics. To enable robust membrane evaluation, a low-cost pressure-driven filtration system was designed and constructed to support extended nanofiltration studies. The findings suggest that near-term industrial impact is most likely in organic-solvent nanofiltration and selective metal-ion adsorption, where COFs’ robustness and modularity provide distinct benefits. Practical constraints—including monomer cost, solvent use, and heating requirements—are examined with potential mitigation pathways. Collectively, the results outline design and manufacturing considerations that chart a pragmatic route from laboratory scale to industrial implementation of COF membranes and sorbents.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2025. p. 80
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2592
Keywords
Covalent organic frameworks, Membrane separation, Scalable fabrication, Energy-efficient separations, COF synthesis, COF processing
National Category
Materials Chemistry Separation Processes
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-567805 (URN)978-91-513-2600-9 (ISBN)
Public defence
2025-11-07, Ångström 4101, Regementsvägen 10, Uppsala, 09:15 (English)
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Supervisors
Available from: 2025-10-16 Created: 2025-09-22 Last updated: 2025-10-16

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Åhlén, MichelleStrömme, MariaXu, Chao

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