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

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

doi:10.1039/d4sc00101j

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

Journal Article · 10 April 2024 · Chemical Science

DOI: https://doi.org/10.1039/d4sc00101j · OSTI ID:2471492

^[1]; Han, Xue ^[2]; Lu, Zhenzhong ^[1];

^[3]; Cheng, Yongqiang ^[4]; Daemen, Luke L. ^[4]; Day, Sarah J. ^[5]; Thompson, Stephen P. ^[5];

^[4];

^[6];

^[1]

University of Manchester (United Kingdom)
University of Manchester (United Kingdom); Beijing Normal University (China)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Laboratory, ISIS Neutron Source
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
University of Manchester (United Kingdom); Peking University, Beijing (China)

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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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Compute and Data Environment for Science (CADES)

Sponsoring Organization:: Engineering and Physical Sciences Research Council (ESPRC); European Research Council (ERC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2471492

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 21 Vol. 15; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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

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