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

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Vitorica-Yrezabal, Iñigo J. and McAnally, Craig A. and Snelgrove, Matthew P. and Warren, Mark R. and Hill, Adrian H. and Thompson, Stephen P. and Quinn, Martin and Mottley, Sam and Mottley, Stephen and Fletcher, Ashleigh J. and Brammer, Lee (2025) Selective CO2 uptake mimics dissolution in highly fluorinated non-porous crystalline materials. Nature Chemistry, 17 (11). pp. 1705-1711. ISSN 1755-4330 (https://doi.org/10.1038/s41557-025-01943-4)

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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.

ORCID iDs

Vitorica-Yrezabal, Iñigo J., McAnally, Craig A. ORCID logoORCID: https://orcid.org/0000-0001-5207-6822, Snelgrove, Matthew P. ORCID logoORCID: https://orcid.org/0000-0003-2665-9084, Warren, Mark R., Hill, Adrian H., Thompson, Stephen P., Quinn, Martin, Mottley, Sam, Mottley, Stephen, Fletcher, Ashleigh J. ORCID logoORCID: https://orcid.org/0000-0003-3915-8887 and Brammer, Lee;
CORE (COnnecting REpositories)