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

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    Type
    Article
    Authors
    Wang, Hu
    Jones, Leighton O. cc
    Hwang, Inhong
    Allen, Marshall J.
    Tao, Daliao
    Lynch, Vincent M.
    Freeman, Benny D. cc
    Khashab, Niveen M. cc
    Schatz, George C cc
    Page, Zachariah A. cc
    Sessler, Jonathan L. cc
    KAUST Department
    Advanced Membranes and Porous Materials Research Center
    Chemical Science Program
    Physical Science and Engineering (PSE) Division
    Smart Hybrid Materials (SHMs) lab
    KAUST Grant Number
    OSR-2019-CRG8-4032
    Date
    2021-11-23
    Embargo End Date
    2022-11-23
    Submitted Date
    2021-09-27
    Permanent link to this record
    http://hdl.handle.net/10754/673749
    
    Metadata
    Show full item record
    Abstract
    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.
    Citation
    Wang, H., Jones, L. O., Hwang, I., Allen, M. J., Tao, D., Lynch, V. M., … Sessler, J. L. (2021). Selective Separation of Lithium Chloride by Organogels Containing Strapped Calix[4]pyrroles. Journal of the American Chemical Society. doi:10.1021/jacs.1c10255
    Sponsors
    J.L.S. and N.M.K. acknowledge support from the King Abdullah University of Science and Technology (KAUST; Grant OSR-2019-CRG8-4032). L.O.J. and G.C.S. were supported by the Center for the Sustainable Separation of Metals (CSSM) funded by the National Science Foundation (Grant No. CHE1925708). Initial support for the work in Austin was also provided by the CSSM. Subsequent support was provided by the Robert A. Welch Foundation (F-0018 and F-2007 to J.L.S. and Z.A.P., respectively). B.D.F.’s work in reviewing the manuscript was supported as part of the Center for Materials for Water and Energy Systems (M-WET), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0019272.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.1c10255
    Additional Links
    https://pubs.acs.org/doi/10.1021/jacs.1c10255
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.1c10255
    Scopus Count
    Collections
    Articles; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Chemical Science Program

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