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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 (i.e., used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Here in this paper, 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 ~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. Lastly, 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]
  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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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.
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. doi:10.1002/anie.201805127.
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. doi:10.1002/anie.201805127. https://www.osti.gov/servlets/purl/1439936.
@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 (i.e., used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Here in this paper, 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 ~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. Lastly, 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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Works referenced in this record:

A Belted Monofacial Ionophore Featuring High Selectivity for Lithium Ion Complexation
journal, May 1999


Calix[4]pyrrole-Based Ion Pair Receptors
journal, June 2014

  • Kim, Sung Kuk; Sessler, Jonathan L.
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar500157a

Preorganization?From Solvents to Spherands
journal, December 1986

  • Cram, Donald J.
  • Angewandte Chemie International Edition in English, Vol. 25, Issue 12
  • DOI: 10.1002/anie.198610393

The Efficient Separation of Lithium Chloride by Acyclic Carrier Molecules
journal, January 2006

  • Ogawa, Shojiro; Morita, Junko; Tsuchiya, Shinji
  • HETEROCYCLES, Vol. 70, Issue 1
  • DOI: 10.3987/COM-06-S(W)37

Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite
journal, August 2016

  • He, Qing; Zhang, Zhan; Brewster, James T.
  • Journal of the American Chemical Society, Vol. 138, Issue 31
  • DOI: 10.1021/jacs.6b05713

Recovery of Lithium from Geothermal Water by Solvent Extraction Technique
journal, April 1992


Heteroditopic Receptors for Ion-Pair Recognition
journal, March 2012

  • McConnell, Anna J.; Beer, Paul D.
  • Angewandte Chemie International Edition, Vol. 51, Issue 21
  • DOI: 10.1002/anie.201107244

Recovery and recycling of lithium: A review
journal, January 2017


Host-guest complexation. 35. Spherands, the first completely preorganized ligand systems
journal, June 1985

  • Cram, Donald J.; Kaneda, Takahiro; Helgeson, Roger C.
  • Journal of the American Chemical Society, Vol. 107, Issue 12
  • DOI: 10.1021/ja00298a040

Synergistic interplay between D2EHPA and TBP towards the extraction of lithium using hollow fiber supported liquid membrane
journal, June 2016

  • Sharma, Ajay D.; Patil, Nivarutti D.; Patwardhan, Ashwin W.
  • Separation Science and Technology, Vol. 51, Issue 13
  • DOI: 10.1080/01496395.2016.1202280

Präorganisation – von Solventien zu Sphäranden
journal, December 1986


New class of lithium ion selective crown ethers with bulky decalin subunits
journal, February 1996


Separation of lithium from sodium in chloride solutions using SSX systems with LIX 54 and Cyanex 923
journal, April 2015


Molecular design and synthesis of a calix[6]crown-based lithium-selective ionophore
journal, June 2000


Ion pair receptors
journal, January 2010

  • Kim, Sung Kuk; Sessler, Jonathan L.
  • Chemical Society Reviews, Vol. 39, Issue 10
  • DOI: 10.1039/c002694h

Editorial
journal, January 2015


A self-assembled, redox-responsive receptor for the selective extraction of LiCl from water
journal, April 2002

  • Piotrowski, H.; Severin, K.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 8
  • DOI: 10.1073/pnas.062663899

Recovery of lithium from alkaline brine by solvent extraction with β-diketone
journal, January 2018


Anion and ion-pair receptor chemistry: highlights from 2000 and 2001
journal, May 2003


Highly Efficient Separation of Lithium Chloride from Seawater
journal, May 2002

  • Tsuchiya, Shinji; Nakatani, Yoko; Ibrahim, Rizwangul
  • Journal of the American Chemical Society, Vol. 124, Issue 18
  • DOI: 10.1021/ja003472m

Selective Complexation of Li + in Water at Neutral pH Using a Self-Assembled Ionophore
journal, November 2003

  • Grote, Zacharias; Lehaire, Marie-Line; Scopelliti, Rosario
  • Journal of the American Chemical Society, Vol. 125, Issue 45
  • DOI: 10.1021/ja036621k

Liquid-liquid extraction of lithium using lipophilic dibenzo-14-crown-4 ether carboxylic acid in hydrophobic room temperature ionic liquid
journal, September 2016


Heteroditope Rezeptoren zur Ionenpaarerkennung
journal, March 2012


Selective Solid−Liquid Extraction of Lithium Halide Salts Using a Ditopic Macrobicyclic Receptor
journal, November 2004

  • Mahoney, Joseph M.; Beatty, Alicia M.; Smith, Bradley D.
  • Inorganic Chemistry, Vol. 43, Issue 24
  • DOI: 10.1021/ic049066b

Molecular mechanical studies of inclusion of alkali cations into anisole spherands
journal, April 1985

  • Kollman, Peter; Wipff, Georges; Singh, U. Chandra
  • Journal of the American Chemical Society, Vol. 107, Issue 8
  • DOI: 10.1021/ja00294a002

    Works referencing / citing this record:

    Präorganisation – von Solventien zu Sphäranden
    journal, December 1986


    Heteroditope Rezeptoren zur Ionenpaarerkennung
    journal, March 2012


    Preorganization?From Solvents to Spherands
    journal, December 1986

    • Cram, Donald J.
    • Angewandte Chemie International Edition in English, Vol. 25, Issue 12
    • DOI: 10.1002/anie.198610393

    Heteroditopic Receptors for Ion-Pair Recognition
    journal, March 2012

    • McConnell, Anna J.; Beer, Paul D.
    • Angewandte Chemie International Edition, Vol. 51, Issue 21
    • DOI: 10.1002/anie.201107244

    Separation of lithium from sodium in chloride solutions using SSX systems with LIX 54 and Cyanex 923
    journal, April 2015


    Liquid-liquid extraction of lithium using lipophilic dibenzo-14-crown-4 ether carboxylic acid in hydrophobic room temperature ionic liquid
    journal, September 2016


    Recovery of lithium from alkaline brine by solvent extraction with β-diketone
    journal, January 2018


    Recovery and recycling of lithium: A review
    journal, January 2017


    Calix[4]pyrrole-Based Ion Pair Receptors
    journal, June 2014

    • Kim, Sung Kuk; Sessler, Jonathan L.
    • Accounts of Chemical Research, Vol. 47, Issue 8
    • DOI: 10.1021/ar500157a

    Selective Solid−Liquid Extraction of Lithium Halide Salts Using a Ditopic Macrobicyclic Receptor
    journal, November 2004

    • Mahoney, Joseph M.; Beatty, Alicia M.; Smith, Bradley D.
    • Inorganic Chemistry, Vol. 43, Issue 24
    • DOI: 10.1021/ic049066b

    Molecular mechanical studies of inclusion of alkali cations into anisole spherands
    journal, April 1985

    • Kollman, Peter; Wipff, Georges; Singh, U. Chandra
    • Journal of the American Chemical Society, Vol. 107, Issue 8
    • DOI: 10.1021/ja00294a002

    Host-guest complexation. 35. Spherands, the first completely preorganized ligand systems
    journal, June 1985

    • Cram, Donald J.; Kaneda, Takahiro; Helgeson, Roger C.
    • Journal of the American Chemical Society, Vol. 107, Issue 12
    • DOI: 10.1021/ja00298a040

    Highly Efficient Separation of Lithium Chloride from Seawater
    journal, May 2002

    • Tsuchiya, Shinji; Nakatani, Yoko; Ibrahim, Rizwangul
    • Journal of the American Chemical Society, Vol. 124, Issue 18
    • DOI: 10.1021/ja003472m

    Selective Complexation of Li + in Water at Neutral pH Using a Self-Assembled Ionophore
    journal, November 2003

    • Grote, Zacharias; Lehaire, Marie-Line; Scopelliti, Rosario
    • Journal of the American Chemical Society, Vol. 125, Issue 45
    • DOI: 10.1021/ja036621k

    Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite
    journal, August 2016

    • He, Qing; Zhang, Zhan; Brewster, James T.
    • Journal of the American Chemical Society, Vol. 138, Issue 31
    • DOI: 10.1021/jacs.6b05713

    Ion pair receptors
    journal, January 2010

    • Kim, Sung Kuk; Sessler, Jonathan L.
    • Chemical Society Reviews, Vol. 39, Issue 10
    • DOI: 10.1039/c002694h

    Thermodynamics of solvation of ions. Part 5.—Gibbs free energy of hydration at 298.15 K
    journal, January 1991


    A self-assembled, redox-responsive receptor for the selective extraction of LiCl from water
    journal, April 2002

    • Piotrowski, H.; Severin, K.
    • Proceedings of the National Academy of Sciences, Vol. 99, Issue 8
    • DOI: 10.1073/pnas.062663899

    Synergistic interplay between D2EHPA and TBP towards the extraction of lithium using hollow fiber supported liquid membrane
    journal, June 2016

    • Sharma, Ajay D.; Patil, Nivarutti D.; Patwardhan, Ashwin W.
    • Separation Science and Technology, Vol. 51, Issue 13
    • DOI: 10.1080/01496395.2016.1202280

    Recovery of Lithium from Geothermal Water by Solvent Extraction Technique
    journal, April 1992


    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


    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