Binding of carbon dioxide and acetylene to free carboxylic acid sites in a metal-organic framework

Christopher Marsh; Xue Han; Zhenzhong Lu; Ivan da Silva; Yongqiang Cheng; Luke L. Daemen; Sarah J. Day; Stephen P. Thompson; Anibal J. Ramirez-Cuesta; Sihai Yang; Martin Schröder

doi:10.1039/d4sc00101j

Binding of carbon dioxide and acetylene to free carboxylic acid sites in a metal-organic framework

Christopher Marsh, Xue Han, Zhenzhong Lu, Ivan da Silva, Yongqiang Cheng, Luke L. Daemen, Sarah J. Day, Stephen P. Thompson, Anibal J. Ramirez-Cuesta, Sihai Yang, Martin Schröder

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

6 Scopus citations

Abstract

The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible -COOH moieties which would normally bind to metal ions within the framework structure. Here, we describe the direct binding of CO₂ and C₂H₂ molecules to the free -COOH sites within the pores of MFM-303(Al). MFM-303(Al) exhibits highly selective adsorption of CO₂ and C₂H₂ with a high selectivity for C₂H₂ over C₂H₄. In situ synchrotron X-ray diffraction and inelastic neutron scattering, coupled with modelling, highlight the cooperative interactions of adsorbed CO₂ and C₂H₂ molecules with free -COOH and -OH sites within MFM-303(Al), thus rationalising the observed high selectivity for gas separation.

Original language	English
Pages (from-to)	8197-8203
Number of pages	7
Journal	Chemical Science
Volume	15
Issue number	21
DOIs	https://doi.org/10.1039/d4sc00101j
State	Published - Apr 10 2024

Funding

We thank EPSRC (EP/I011870), the Royal Society, University of Manchester, BNLMS and Peking University for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement No. 742401, NANOCHEM). We are grateful to Diamond Light Source for access to Beamline I11. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Computing resources for neutron data analysis were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL.

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title = "Binding of carbon dioxide and acetylene to free carboxylic acid sites in a metal-organic framework",

abstract = "The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible -COOH moieties which would normally bind to metal ions within the framework structure. Here, we describe the direct binding of CO2 and C2H2 molecules to the free -COOH sites within the pores of MFM-303(Al). MFM-303(Al) exhibits highly selective adsorption of CO2 and C2H2 with a high selectivity for C2H2 over C2H4. In situ synchrotron X-ray diffraction and inelastic neutron scattering, coupled with modelling, highlight the cooperative interactions of adsorbed CO2 and C2H2 molecules with free -COOH and -OH sites within MFM-303(Al), thus rationalising the observed high selectivity for gas separation.",

author = "Christopher Marsh and Xue Han and Zhenzhong Lu and {da Silva}, Ivan and Yongqiang Cheng and Daemen, {Luke L.} and Day, {Sarah J.} and Thompson, {Stephen P.} and Ramirez-Cuesta, {Anibal J.} and Sihai Yang and Martin Schr{\"o}der",

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doi = "10.1039/d4sc00101j",

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T1 - Binding of carbon dioxide and acetylene to free carboxylic acid sites in a metal-organic framework

AU - Marsh, Christopher

AU - Han, Xue

AU - Lu, Zhenzhong

AU - da Silva, Ivan

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Day, Sarah J.

AU - Thompson, Stephen P.

AU - Ramirez-Cuesta, Anibal J.

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2024/4/10

Y1 - 2024/4/10

N2 - The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible -COOH moieties which would normally bind to metal ions within the framework structure. Here, we describe the direct binding of CO2 and C2H2 molecules to the free -COOH sites within the pores of MFM-303(Al). MFM-303(Al) exhibits highly selective adsorption of CO2 and C2H2 with a high selectivity for C2H2 over C2H4. In situ synchrotron X-ray diffraction and inelastic neutron scattering, coupled with modelling, highlight the cooperative interactions of adsorbed CO2 and C2H2 molecules with free -COOH and -OH sites within MFM-303(Al), thus rationalising the observed high selectivity for gas separation.

AB - The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible -COOH moieties which would normally bind to metal ions within the framework structure. Here, we describe the direct binding of CO2 and C2H2 molecules to the free -COOH sites within the pores of MFM-303(Al). MFM-303(Al) exhibits highly selective adsorption of CO2 and C2H2 with a high selectivity for C2H2 over C2H4. In situ synchrotron X-ray diffraction and inelastic neutron scattering, coupled with modelling, highlight the cooperative interactions of adsorbed CO2 and C2H2 molecules with free -COOH and -OH sites within MFM-303(Al), thus rationalising the observed high selectivity for gas separation.

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DO - 10.1039/d4sc00101j

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JF - Chemical Science

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ER -

Binding of carbon dioxide and acetylene to free carboxylic acid sites in a metal-organic framework

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