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Title: Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters

Abstract

Ligands that can discriminate between individual rare earth elements are important for production of these critical elements. A set of aryl-vinyl phosphonic acid ligands for extracting rare earth elements were designed and synthesized under the hypothesis that the strength of the rare earth-ligand interactions could be tuned by changing the dipole moment of the ligand. The ligands were synthesized via a two-step reaction procedure using a Heck coupling reaction to functionalize vinyl phosphonic acid, followed by Steglich esterification to obtain high-purity styryl phosphonic acid monoesters with varying dipole moments along the P-C bond. The metal binding strength and composition of the rare earth complexes formed with these styryl phosphonic acid monoesters were experimentally studied by liquid-liquid extraction techniques, while DFT calculations were performed to determine the dipole moments of the free and complexed ligands and the electronic structure of the complexes formed. All three prepared ligands were much stronger extracting agents for europium(III) than the dialkylphosphonic acids usually used for this separation. However, the order of increasing extraction strength was found to match the order of the decreasing calculated dipole moment along the P-C bond of the three styryl-based ligands, rather than correlating with increasing ligand basicity, as reflected bymore » the pKa of the ligands. Finally, these findings suggest that this approach can be used to systematically alter the extraction strength of aromatic phosphonic monoesters for rare earth element purification.« less

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]
+ Show Author Affiliations
  1. Colorado School of Mines, Golden, CO (United States)
  2. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  3. National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Institute (RSEI)
  4. Colorado School of Mines, Golden, CO (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
2006602
Report Number(s):
NREL/JA-2C00-87496
Journal ID: ISSN 0020-1669; MainId:88271;UUID:b399b30f-47fe-4ad5-a3cd-b5cd07da84fe;MainAdminID:70627
Grant/Contract Number:  
AC36-08GO28308; NE0008582
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 62; Journal Issue: 40; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; functionalized ligand; lanthanide; rare earth metals; separations

Citation Formats

Kuvayskaya, Anastasia, Mallos, Thomas J., Douair, Iskander, Chang, Christopher, Larsen, Ross E., Jensen, Mark P., and Sellinger, Alan. Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters. United States: N. p., 2023. Web. doi:10.1021/acs.inorgchem.3c01714.
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Kuvayskaya, Anastasia, Mallos, Thomas J., Douair, Iskander, Chang, Christopher, Larsen, Ross E., Jensen, Mark P., & Sellinger, Alan. Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters. United States. https://doi.org/10.1021/acs.inorgchem.3c01714
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Kuvayskaya, Anastasia, Mallos, Thomas J., Douair, Iskander, Chang, Christopher, Larsen, Ross E., Jensen, Mark P., and Sellinger, Alan. Tue . "Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters". United States. https://doi.org/10.1021/acs.inorgchem.3c01714.
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@article{osti_2006602,
title = {Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters},
author = {Kuvayskaya, Anastasia and Mallos, Thomas J. and Douair, Iskander and Chang, Christopher and Larsen, Ross E. and Jensen, Mark P. and Sellinger, Alan},
abstractNote = {Ligands that can discriminate between individual rare earth elements are important for production of these critical elements. A set of aryl-vinyl phosphonic acid ligands for extracting rare earth elements were designed and synthesized under the hypothesis that the strength of the rare earth-ligand interactions could be tuned by changing the dipole moment of the ligand. The ligands were synthesized via a two-step reaction procedure using a Heck coupling reaction to functionalize vinyl phosphonic acid, followed by Steglich esterification to obtain high-purity styryl phosphonic acid monoesters with varying dipole moments along the P-C bond. The metal binding strength and composition of the rare earth complexes formed with these styryl phosphonic acid monoesters were experimentally studied by liquid-liquid extraction techniques, while DFT calculations were performed to determine the dipole moments of the free and complexed ligands and the electronic structure of the complexes formed. All three prepared ligands were much stronger extracting agents for europium(III) than the dialkylphosphonic acids usually used for this separation. However, the order of increasing extraction strength was found to match the order of the decreasing calculated dipole moment along the P-C bond of the three styryl-based ligands, rather than correlating with increasing ligand basicity, as reflected by the pKa of the ligands. Finally, these findings suggest that this approach can be used to systematically alter the extraction strength of aromatic phosphonic monoesters for rare earth element purification.},
doi = {10.1021/acs.inorgchem.3c01714},
journal = {Inorganic Chemistry},
number = 40,
volume = 62,
place = {United States},
year = {Tue Sep 26 00:00:00 EDT 2023},
month = {Tue Sep 26 00:00:00 EDT 2023}
}
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