Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials

Abstract

Separation of CO2 from gas mixtures is important in applications such as CH4 gas purification and blue hydrogen production. Here we report selective CO2 uptake by a family of flexible silver coordination polymers (AgCPs) that are ostensibly non-porous but exhibit latent porosity to CO2 above a gate pressure, through a mechanism akin to dissolution in fluoroalkanes. The CO2 sorption properties are rationally modified by changing the perfluoroalkyl chain length of the constituent perfluorocarboxylate ligands. The AgCPs do not take up CH4 owing to failure of the dissolution mechanism, consistent with alkane–perfluoroalkane immiscibility. In situ single-crystal and powder X-ray diffraction enable direct visualization of the CO2 molecule binding domains. These techniques also reveal associated structural changes in the AgCPs and confirm the gating mechanism of CO2 uptake. The combination of perfluoroalkylcarboxylate ligands with the flexible silver(I) coordination sphere generates highly fluorinated but mobile regions of the crystals that play an integral role in the selective uptake of CO2 over CH4.

Metadata

Item Type:	Article
Authors/Creators:	Vitórica-Yrezábal, I.J. https://orcid.org/0000-0001-8806-150X McAnally, C.A. https://orcid.org/0009-0007-7444-6311 Snelgrove, M.P. https://orcid.org/0000-0003-2665-9084 Warren, M.R. https://orcid.org/0000-0003-1326-0744 Hill, A.H. https://orcid.org/0000-0003-1760-2967 Thompson, S.P. https://orcid.org/0000-0001-9627-2606 Quinn, M. Mottley, S. Mottley, S. Fletcher, A.J. https://orcid.org/0000-0003-3915-8887 Brammer, L. https://orcid.org/0000-0001-6435-7197
Copyright, Publisher and Additional Information:	© The Author(s) 2025. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, 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 changes were made. 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/4.0/.
Keywords:	Metal–organic frameworks; Solid-state chemistry; Supramolecular chemistry
Dates:	Submitted: 14 June 2024 Accepted: 14 August 2025 Published (online): 14 October 2025 Published: November 2025
Institution:	The University of Sheffield
Academic Units:	The University of Sheffield > Faculty of Science (Sheffield) > School of Mathematical and Physical Sciences
Funding Information:	Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/F02195X/1
Date Deposited:	31 Oct 2025 15:17
Last Modified:	31 Oct 2025 15:17
Status:	Published
Publisher:	Springer Science and Business Media LLC
Refereed:	Yes
Identification Number:	10.1038/s41557-025-01943-4
Related URLs:	PubMed URL
Open Archives Initiative ID (OAI ID):	oai:eprints.whiterose.ac.uk:233727

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Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials

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