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CO2 Behavior in a Highly Selective Ultramicroporous Framework: Insights from Single-Crystal X-ray Diffraction and Solid-State Nuclear Magnetic Resonance Spectroscopy

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    CO2 Behavior in a Highly Selective Ultramicroporous Framework: Insights from Single-Crystal X-ray Diffraction and Solid-State Nuclear Magnetic Resonance Spectroscopy
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    • Bligh E. Desveaux
      Bligh E. Desveaux
      Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
      More by Bligh E. Desveaux
    • Y. T. Angel Wong
      Y. T. Angel Wong
      Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
      More by Y. T. Angel Wong
      Orcidhttp://orcid.org/0000-0003-0118-1440
    • Bryan E. G. Lucier
      Bryan E. G. Lucier
      Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
      More by Bryan E. G. Lucier
      Orcidhttp://orcid.org/0000-0002-9682-4324
    • Victor V. Terskikh
      Victor V. Terskikh
      Department of Chemistry, University of Ottawa, 75 Laurier Ave E, Ottawa, Ontario K1N 6N5, Canada
      More by Victor V. Terskikh
      Orcidhttp://orcid.org/0000-0003-1514-2610
    • Paul D. Boyle
      Paul D. Boyle
      Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
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    • Shan Jiang
      Shan Jiang
      Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
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    • Yining Huang*
      Yining Huang
      Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, Ontario N6A 5B7, Canada
      *E-mail: [email protected]. Webpage: http://publish.uwo.ca/~yhuang/index.htm.
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      Orcidhttp://orcid.org/0000-0001-9265-5896
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2019, 123, 29, 17798–17807
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    https://doi.org/10.1021/acs.jpcc.9b03221
    Published July 2, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Metal–organic frameworks (MOFs) are a class of porous materials that have attracted much attention for gas adsorption applications. The ultramicroporous SIFSIX-3-Zn MOF, made up of zinc and pyrazine sheets pillared into a three-dimensional framework by hexafluorosilicate ions, has displayed remarkable carbon dioxide (CO2) capture abilities. Even though the CO2 adsorption capability of SIFSIX-3-Zn is known, a detailed experimental description of the CO2-loaded SIFSIX-3-Zn structure and the behavior of the adsorbed CO2 guests is yet to be reported. In this work, CO2 adsorption in SIFSIX-3-Zn is examined at the molecular level. Single-crystal X-ray diffraction (SCXRD) was employed to identify the CO2 adsorption sites. The crystal structure of CO2-loaded MOF was subsequently compared to that of the as-made SIFSIX-3-Zn, which shows that the crystal symmetry of the MOF is guest-dependent, although the framework topology remains the same. 13C, 19F, 29Si, and 67Zn solid-state nuclear magnetic resonance (SSNMR) spectroscopy was also performed to investigate the as-made, activated, and CO2-loaded SIFSIX-3-Zn. The SSNMR results reveal new insights into the effect of guest inclusion on the structure of the three SIFISIX-3-Zn phases. We have also examined CO2 dynamics in SIFSIX-3-Zn via variable-temperature 13C SSNMR spectroscopy. Adsorbed CO2 displays unusually hindered mobility, which is affected very little by temperature. This unique motional behavior is attributed to the strong CO2–MOF interactions imposed by the ultramicroporosity of the framework. The combination of SCXRD and SSNMR results clearly show that the synergistic interactions of framework hydrogen and fluorine atoms with CO2 inside the MOF is a major factor that leads to the excellent CO2 adsorption capability of SIFSIX-3-Zn.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.9b03221.

    • Crystal structure of the as-made SIFSIX-3-Zn at 298 K (Figure S1); experimental and simulated PXRD patterns of the as-made SIFSIX-3-Zn (Figure S2); SCXRD data for the CO2-loaded SIFSIX-3-Zn at 110 K (Tables S1–S7); ORTEP drawing of the CO2-loaded SIFSIX-3-Zn (Figure S3); comparison of bond angles in the as-made and CO2-loaded SIFSIX-3-Zn (Table S8); asymmetric unit of the CO2-loaded and as-made SIFSIX-3-Zn (Figure S4); 19F and 29Si SSNMR results and discussion; 19F and 1H → 29Si CP/MAS SSNMR spectra of the as-made, activated and CO2-loaded SIFSIX-3-Zn (Figure S5); δiso(19F) and δiso(29Si) values of the as-made, activated, and CO2-loaded SIFSIX-3-Zn (Table S9); influence of temperature on the motional rates of CO2 in SIFSIX-3-Zn; static 13CO2 SSNMR spectra simulated using different motional rates (Figure S6) (PDF)

    • Crystallographic data for n17104 (CIF)

    • Datablock: n17104 (PDF)

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    This article is cited by 19 publications.

    1. Francesca Nardelli, Francesca Nerli, Elisa Della Latta, Francesca Martini, Marco Geppi, Marco Taddei, Lucia Calucci. Unveiling CO2 Dynamics in Perfluorinated Cerium-Based Metal–Organic Frameworks with UiO-66 and MIL-140 Topologies by Solid State NMR. The Journal of Physical Chemistry C 2024, 128 (16) , 6887-6896. https://doi.org/10.1021/acs.jpcc.4c00483
    2. Vinicius Martins, Bryan E.G. Lucier, Zhiqang Liu, Heng Liang, Anmin Zheng, Victor V. Terskikh, Wanli Zhang, Bligh E. Desveaux, Yining Huang. Cold, Hot, Dry, and Wet: Locations and Dynamics of CO2 and H2O Co-Adsorbed in an Ultramicroporous MOF. Inorganic Chemistry 2023, 62 (28) , 11152-11167. https://doi.org/10.1021/acs.inorgchem.3c01251
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    13. Ana Carolina Cons Bacilla, Ryusuke Futamura, Yasuhiro Sugiyama, Takahiro Ueda, Taku Iiyama. Formation of amorphous and quasi-two-dimensional microcrystalline structures of CO2 in activated carbon pores at low temperatures. Carbon 2022, 193 , 88-97. https://doi.org/10.1016/j.carbon.2022.02.061
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    15. Yingxian Li, Wanli Zhang, Yining Huang. Two open metal sites on the same metal: Dynamics of CO2 in MOF UTSA-74. Magnetic Resonance Letters 2021, 1 (2) , 121-130. https://doi.org/10.1016/j.mrl.2021.100023
    16. Renata Avena Maia, Benoît Louis, Wanlin Gao, Qiang Wang. CO 2 adsorption mechanisms on MOFs: a case study of open metal sites, ultra-microporosity and flexible framework. Reaction Chemistry & Engineering 2021, 6 (7) , 1118-1133. https://doi.org/10.1039/D1RE00090J
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    19. Marko Bertmer. Solid-state NMR of small molecule adsorption in metal–organic frameworks (MOFs). 2020, 1-64. https://doi.org/10.1016/bs.arnmr.2020.07.003
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2019, 123, 29, 17798–17807
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.9b03221
    Published July 2, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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