DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion‐Pair Receptor

Abstract

Abstract Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid–liquid extraction‐based removal of cesium salts, specifically CsOH and Cs 2 CO 3 , from highly basic media. A multitopic ion‐pair receptor ( 2 ) is used that can recognize and extract the hydroxide and carbonate anions as their cesium salts, as confirmed by 1 H NMR spectroscopic titrations, ICP‐MS, single‐crystal structural analyses, and theoretical calculations. A sharp increase in the pH and cesium concentrations in the receiving phase is observed when receptor 2 is employed as a carrier in U‐tube experiments involving the transport of CsOH through an intervening chloroform layer. The pH of the source phase likewise decreases.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry University of Texas at Austin 105 E. 24th Street A5300 Austin TX 78712-1224 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1373982
Grant/Contract Number:  
FG02-01ER15186
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Name: Angewandte Chemie Journal Volume: 129 Journal Issue: 43; Journal ID: ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

He, Qing, Peters, Gretchen Marie, Lynch, Vincent M., and Sessler, Jonathan L. Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion‐Pair Receptor. Germany: N. p., 2017. Web. doi:10.1002/ange.201705788.
He, Qing, Peters, Gretchen Marie, Lynch, Vincent M., & Sessler, Jonathan L. Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion‐Pair Receptor. Germany. https://doi.org/10.1002/ange.201705788
He, Qing, Peters, Gretchen Marie, Lynch, Vincent M., and Sessler, Jonathan L. Fri . "Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion‐Pair Receptor". Germany. https://doi.org/10.1002/ange.201705788.
@article{osti_1373982,
title = {Recognition and Extraction of Cesium Hydroxide and Carbonate by Using a Neutral Multitopic Ion‐Pair Receptor},
author = {He, Qing and Peters, Gretchen Marie and Lynch, Vincent M. and Sessler, Jonathan L.},
abstractNote = {Abstract Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid–liquid extraction‐based removal of cesium salts, specifically CsOH and Cs 2 CO 3 , from highly basic media. A multitopic ion‐pair receptor ( 2 ) is used that can recognize and extract the hydroxide and carbonate anions as their cesium salts, as confirmed by 1 H NMR spectroscopic titrations, ICP‐MS, single‐crystal structural analyses, and theoretical calculations. A sharp increase in the pH and cesium concentrations in the receiving phase is observed when receptor 2 is employed as a carrier in U‐tube experiments involving the transport of CsOH through an intervening chloroform layer. The pH of the source phase likewise decreases.},
doi = {10.1002/ange.201705788},
journal = {Angewandte Chemie},
number = 43,
volume = 129,
place = {Germany},
year = {Fri Aug 04 00:00:00 EDT 2017},
month = {Fri Aug 04 00:00:00 EDT 2017}
}

Works referenced in this record:

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

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

Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion
journal, November 2015

  • Nava, Matthew; Lopez, Nazario; Müller, Peter
  • Journal of the American Chemical Society, Vol. 137, Issue 46
  • DOI: 10.1021/jacs.5b08495

A Robust Alkaline-Side csex Solvent Suitable for Removing Cesium from Savannah River high Level Waste#
journal, November 2000

  • Bonnesen, Peter V.; Delmau, Lætitia H.; Moyer, Bruce A.
  • Solvent Extraction and Ion Exchange, Vol. 18, Issue 6
  • DOI: 10.1080/07366290008934723

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

Calix[4]pyrroles:  Old Yet New Anion-Binding Agents
journal, January 1996

  • Gale, Philip A.; Sessler, Jonathan L.; Král, Vladimír
  • Journal of the American Chemical Society, Vol. 118, Issue 21
  • DOI: 10.1021/ja960307r

Synthetic transporters for sulfate: a new method for the direct detection of lipid bilayer sulfate transport
journal, January 2014

  • Busschaert, Nathalie; Karagiannidis, Louise E.; Wenzel, Marco
  • Chemical Science, Vol. 5, Issue 3
  • DOI: 10.1039/c3sc52006d

Selective Separation of Hydroxide from Alkaline Nuclear Tank Waste by Liquid−Liquid Extraction with Weak Hydroxy Acids
journal, April 2002

  • Chambliss, C. Kevin; Haverlock, Tamara J.; Bonnesen, Peter V.
  • Environmental Science & Technology, Vol. 36, Issue 8
  • DOI: 10.1021/es011124u

Ion pair receptors
journal, January 2010

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

Calix[4]pyrrole: An Old yet New Ion-Pair Receptor
journal, April 2005

  • Custelcean, Radu; Delmau, Lætitia H.; Moyer, Bruce A.
  • Angewandte Chemie, Vol. 117, Issue 17
  • DOI: 10.1002/ange.200462945

Lipophilic, Mono-ionizable, Calix[4]arene-bis(benzocrown-6) Compounds for Solvent Extraction of Cesium from Nuclear Wastes: Synthesis and Evaluation
journal, May 2013

  • Zhou, Hui; Connery, Kathryn E.; Bartsch, Richard A.
  • Solvent Extraction and Ion Exchange, Vol. 31, Issue 7
  • DOI: 10.1080/07366299.2013.806754

A Case for Molecular Recognition in Nuclear Separations: Sulfate Separation from Nuclear Wastes
journal, June 2012

  • Moyer, Bruce A.; Custelcean, Radu; Hay, Benjamin P.
  • Inorganic Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/ic3016832

Use of Calix[4]-bis-2,3-naphthocrown-6 for Separation of Cesium from Pressurized Heavy Water Reactor Simulated High Level Waste Solutions (PHWR-SHLW)
journal, October 2009

  • Raut, D. R.; Mohapatra, P. K.; Ansari, S. A.
  • Separation Science and Technology, Vol. 44, Issue 15
  • DOI: 10.1080/01496390903183352

Supramolecular Chemistry
book, January 2009


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


Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion
journal, October 2014

  • Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J.
  • Journal of the American Chemical Society, Vol. 136, Issue 42
  • DOI: 10.1021/ja5086996

The first supramolecular ion triplet complex
journal, January 2010

  • Eckelmann, Jens; Saggiomo, Vittorio; Sönnichsen, Frank D.
  • New Journal of Chemistry, Vol. 34, Issue 7
  • DOI: 10.1039/c0nj00160k

Recognition and separation of sulfate anions
journal, January 2012

  • Ravikumar, I.; Ghosh, Pradyut
  • Chemical Society Reviews, Vol. 41, Issue 8
  • DOI: 10.1039/c2cs15293b

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


Calix[4]pyrrole:  A New Ion-Pair Receptor As Demonstrated by Liquid−Liquid Extraction
journal, March 2008

  • Wintergerst, Matthieu P.; Levitskaia, Tatiana G.; Moyer, Bruce A.
  • Journal of the American Chemical Society, Vol. 130, Issue 12
  • DOI: 10.1021/ja7102179

Sulfate-Selective Binding and Sensing of a Fluorescent [3]Rotaxane Host System
journal, October 2012

  • Langton, Matthew J.; Beer, Paul D.
  • Chemistry - A European Journal, Vol. 18, Issue 45
  • DOI: 10.1002/chem.201202204

Heteroditope Rezeptoren zur Ionenpaarerkennung
journal, March 2012


Calixarene-based Extraction Chromatographic Separation of 135 Cs and 137 Cs in Environmental and Waste Samples Prior to Sector Field ICP-MS Analysis
journal, November 2014

  • Russell, Ben C.; Warwick, Phil E.; Croudace, Ian W.
  • Analytical Chemistry, Vol. 86, Issue 23
  • DOI: 10.1021/ac5036988

Calix[4]pyrrole: An Old yet New Ion-Pair Receptor
journal, April 2005

  • Custelcean, Radu; Delmau, Lætitia H.; Moyer, Bruce A.
  • Angewandte Chemie International Edition, Vol. 44, Issue 17
  • DOI: 10.1002/anie.200462945

A benzocrown-6-calix[4]arene methacrylate copolymer: Selective extraction of caesium ions from a multi-component system
journal, January 2010

  • Rambo, Brett M.; Kim, Sung Kuk; Kim, Jong Seung
  • Chemical Science, Vol. 1, Issue 6
  • DOI: 10.1039/c0sc00396d

Calix[6]arene-Based Cascade Complexes of Organic Ion Triplets Stable in a Protic Solvent
journal, September 2010

  • Moerkerke, Steven; Ménand, Mickaël; Jabin, Ivan
  • Chemistry - A European Journal, Vol. 16, Issue 38
  • DOI: 10.1002/chem.201001193