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Title: Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles

Abstract

LiCl is a classic hard ion salt that is present in lithium-rich brines and a key component in end-of-life materials (that is, used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Herein, we describe two ditopic calix[4]pyrrole-based ion-pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl/KCl salt mixture containing as little as 1% LiCl with circa 100% selectivity, while receptor 3 achieved similar separations when the LiCl level was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl>NaCl>LiCl. In contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.

Authors:
 [1]; ORCiD logo [2];  [3];  [1];  [3]; ORCiD logo [2];  [4]
+ Show Author Affiliations
  1. Univ. of Texas, Austin, TX (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  3. Gyeongsang National University (GNU), Jinju (Korea). Chemistry and Research Institute of Natural Science
  4. Univ. of Texas, Austin, TX (United States). Department of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Texas, Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1439936
Alternate Identifier(s):
OSTI ID: 1455075; OSTI ID: 1598669
Grant/Contract Number:  
AC05-00OR22725; FG02-01ER15186
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 37; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; ion-pair receptor; solid-liquid extraction; lithium choride; calix[4]pyrrole; liquid-liquid extraction

Citation Formats

He, Qing, Williams, Neil J., Oh, Ju, Lynch, Vincent M., Kim, Sung Kuk, Moyer, Bruce A., and Sessler, Jonathan L. Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles. United States: N. p., 2018. Web. doi:10.1002/anie.201805127.
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He, Qing, Williams, Neil J., Oh, Ju, Lynch, Vincent M., Kim, Sung Kuk, Moyer, Bruce A., & Sessler, Jonathan L. Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles. United States. https://doi.org/10.1002/anie.201805127
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He, Qing, Williams, Neil J., Oh, Ju, Lynch, Vincent M., Kim, Sung Kuk, Moyer, Bruce A., and Sessler, Jonathan L. Fri . "Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles". United States. https://doi.org/10.1002/anie.201805127. https://www.osti.gov/servlets/purl/1439936.
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@article{osti_1439936,
title = {Selective Solid-liquid Extraction and Liquid-liquid Extraction of Lithium Chloride using Strapped Calix[4]pyrroles},
author = {He, Qing and Williams, Neil J. and Oh, Ju and Lynch, Vincent M. and Kim, Sung Kuk and Moyer, Bruce A. and Sessler, Jonathan L.},
abstractNote = {LiCl is a classic hard ion salt that is present in lithium-rich brines and a key component in end-of-life materials (that is, used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Herein, we describe two ditopic calix[4]pyrrole-based ion-pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl/KCl salt mixture containing as little as 1% LiCl with circa 100% selectivity, while receptor 3 achieved similar separations when the LiCl level was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl>NaCl>LiCl. In contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.},
doi = {10.1002/anie.201805127},
journal = {Angewandte Chemie (International Edition)},
number = 37,
volume = 57,
place = {United States},
year = {2018},
month = {5}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/anie.201805127
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Cited by: 57 works
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Figures / Tables:

Figure 1 Figure 1: Chemical structures of receptors 1–3.
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    Works referencing / citing this record:

    Removal of Anions from Aqueous Media by Means of a Thermoresponsive Calix[4]pyrrole Amphiphilic Polymer
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    • Ji, Xiaofan; Guo, Chenxing; Chen, Wei
    • Chemistry - A European Journal, Vol. 24, Issue 59
    • DOI: 10.1002/chem.201804335

    Optimizing radionuclide sequestration in anion nanotraps with record pertechnetate sorption
    journal, April 2019

    Highly efficient synthesis of hydrogen-bonded aromatic tetramers as macrocyclic receptors for selective recognition of lithium ions
    journal, January 2019

    • Guo, Xuwen; Yang, Yizhou; Peng, Zhiyong
    • Organic Chemistry Frontiers, Vol. 6, Issue 15
    • DOI: 10.1039/c9qo00612e

    Cesium halide ion pair recognition by a pyrrole strapped Calix[4]pyrrole
    journal, October 2018

    The Effect of Substitution Pattern on Binding Ability in Regioisomeric Ion Pair Receptors Based on an Aminobenzoic Platform
    journal, August 2019

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