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Selective Separation of Lithium Chloride by Organogels Containing Strapped Calix[4]pyrroles

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    Selective Separation of Lithium Chloride by Organogels Containing Strapped Calix[4]pyrroles
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    • Hu Wang
      Hu Wang
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
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    • Leighton O. Jones
      Leighton O. Jones
      Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
      More by Leighton O. Jones
      Orcidhttps://orcid.org/0000-0001-6657-2632
    • Inhong Hwang
      Inhong Hwang
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
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    • Marshall J. Allen
      Marshall J. Allen
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
      McKetta Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712, United States
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    • Daliao Tao
      Daliao Tao
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
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    • Vincent M. Lynch
      Vincent M. Lynch
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
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    • Benny D. Freeman
      Benny D. Freeman
      McKetta Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712, United States
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      Orcidhttps://orcid.org/0000-0003-2779-7788
    • Niveen M. Khashab
      Niveen M. Khashab
      Smart Hybrid Materials (SHMs) Laboratory Advanced Membranes and Porous Materials Center, King Abdullah University of Science and Technology, Thuwal, 23955, Saudi Arabia
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      Orcidhttps://orcid.org/0000-0003-2728-0666
    • George C. Schatz*
      George C. Schatz
      Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-5837-4740
    • Zachariah A. Page*
      Zachariah A. Page
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0002-1013-5422
    • Jonathan L. Sessler*
      Jonathan L. Sessler
      Department of Chemistry, 105 East 24th Street, Stop A5300, The University of Texas at Austin, Austin, Texas 78712, United States
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0002-9576-1325
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 48, 20403–20410
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    https://doi.org/10.1021/jacs.1c10255
    Published November 23, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    Reported herein are two functionalized crown ether strapped calix[4]pyrroles, H1 and H2. As inferred from competitive salt binding experiments carried out in nitrobenzene-d5 and acetonitrile-d3, these hosts capture LiCl selectively over four other test salts, viz. NaCl, KCl, MgCl2, and CaCl2. Support for the selectivity came from density functional theory (DFT) calculations carried out in a solvent continuum. These theoretical analyses revealed a higher innate affinity for LiCl in the case of H1, but a greater selectivity relative to NaCl in the case of H2, recapitulating that observed experimentally. Receptors H1 and H2 were outfitted with methacrylate handles and subject to copolymerization with acrylate monomers and cross-linkers to yield gels, G1 and G2, respectively. These two gels were found to adsorb lithium chloride preferentially from an acetonitrile solution containing a mixture of LiCl, NaCl, KCl, MgCl2, and CaCl2 and then release the lithium chloride in methanol. The gels could then be recycled for reuse in the selective adsorption of LiCl. As such, the present study highlights the use of solvent polarity switching to drive separations with potential applications in lithium purification and recycling.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c10255.

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    CCDC 2107218 and 2107227 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 48, 20403–20410
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c10255
    Published November 23, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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