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

Iñigo J. Vitorica-Yrezabal; Craig A. McAnally; Matthew P. Snelgrove; Mark R. Warren; Adrian H. Hill; Stephen P. Thompson; Martin Quinn; Sam Mottley; Stephen Mottley; Ashleigh J. Fletcher; Lee Brammer

doi:10.1038/s41557-025-01943-4

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

Iñigo J. Vitorica-Yrezabal^*, Craig A. McAnally, Matthew P. Snelgrove, Mark R. Warren, Adrian H. Hill, Stephen P. Thompson, Martin Quinn, Sam Mottley, Stephen Mottley, Ashleigh J. Fletcher, Lee Brammer^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	1705-1711
Number of pages	15
Journal	Nature Chemistry
Volume	17
Issue number	11
Early online date	14 Oct 2025
DOIs	https://doi.org/10.1038/s41557-025-01943-4
Publication status	Published - 14 Oct 2025

Funding

We are grateful to the Diamond Light Source for access to the Beamlines I11 and I19, and ESRF for access to beamline ID31 (currently ID22). We acknowledge the support of The University of Manchester X-ray diffraction service members and are grateful to The University of Manchester mechanical and electronic workshops for their assistance in the construction of the gas cell/rig instrumentation. We thank A. Harvey and D. J. Ashworth (University of Strathclyde) for assistance in undertaking adsorption measurements. We thank EPSRC for funding via grant EP/F02195X/1 (L.B.), a DTP award supporting CAM (grant EP/L505080/1 to A.J.F.) and a doctoral prize fellowship for I.J.V.-Y. We also thank the University of Manchester for funding.

Keywords

dissolving CO2
gas purification
molecular separations
crystallization

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1038/s41557-025-01943-4Licence: CC BY 4.0

Vitorica-Yrezabal-etal-NC-2025-Selective-CO2-uptake-mimics-dissolution-in-highly-fluorinatedFinal published version, 4.04 MBLicence: CC BY 4.0

Cite this

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title = "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.",

keywords = "dissolving CO2, gas purification, molecular separations, crystallization",

author = "Vitorica-Yrezabal, \{I{\~n}igo J.\} and McAnally, \{Craig A.\} and Snelgrove, \{Matthew P.\} and Warren, \{Mark R.\} and Hill, \{Adrian H.\} and Thompson, \{Stephen P.\} and Martin Quinn and Sam Mottley and Stephen Mottley and Fletcher, \{Ashleigh J.\} and Lee Brammer",

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doi = "10.1038/s41557-025-01943-4",

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T1 - Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials

AU - Vitorica-Yrezabal, Iñigo J.

AU - McAnally, Craig A.

AU - Snelgrove, Matthew P.

AU - Warren, Mark R.

AU - Hill, Adrian H.

AU - Thompson, Stephen P.

AU - Quinn, Martin

AU - Mottley, Sam

AU - Mottley, Stephen

AU - Fletcher, Ashleigh J.

AU - Brammer, Lee

PY - 2025/10/14

Y1 - 2025/10/14

N2 - 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.

AB - 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.

KW - dissolving CO2

KW - gas purification

KW - molecular separations

KW - crystallization

UR - https://doi.org/10.15131/shef.data.29620916.v1

U2 - 10.1038/s41557-025-01943-4

DO - 10.1038/s41557-025-01943-4

M3 - Article

SN - 1755-4330

VL - 17

SP - 1705

EP - 1711

JO - Nature Chemistry

JF - Nature Chemistry

IS - 11

ER -

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

Abstract

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Keywords

UN SDGs

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Data for: "Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials"

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

Abstract

Funding

Keywords

UN SDGs

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Data for: "Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials"

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