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

Kuvayskaya, Anastasia; Mallos, Thomas J.; Douair, Iskander; Chang, Christopher; Larsen, Ross E.; Jensen, Mark P.; Sellinger, Alan

doi:10.1021/acs.inorgchem.3c01714

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

Journal Article · Tue Sep 26 00:00:00 EDT 2023 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.3c01714· OSTI ID:2006602

^[1]; Mallos, Thomas J. ^[1]; Douair, Iskander ^[2];

^[2];

^[3];

^[1];

^[4]

Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Institute (RSEI)
Colorado School of Mines, Golden, CO (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)

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 pK_a 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.

This content will become publicly available on Thu Sep 26 00:00:00 EDT 2024

Cite

Export

Save

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308; NE0008582

OSTI ID:: 2006602

Report Number(s):: NREL/JA-2C00-87496; MainId:88271; UUID:b399b30f-47fe-4ad5-a3cd-b5cd07da84fe; MainAdminID:70627

Journal Information:: Inorganic Chemistry, Vol. 62, Issue 40; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (66)

Comparative liquid-liquid extraction behaviour of europium (II) and europium (III) Peppard, D. F.; Horwitz, E. P.; Mason, G. W. Journal of Inorganic and Nuclear Chemistry, Vol. 24, Issue 4 https://doi.org/10.1016/0022-1902(62)80039-6	journal	April 1962
5,10-Dihydroindolo[3,2- b ]indole-Based Copolymers with Alternating Donor and Acceptor Moieties for Organic Photovoltaics Owczarczyk, Zbyslaw R.; Braunecker, Wade A.; Garcia, Andres Macromolecules, Vol. 46, Issue 4 https://doi.org/10.1021/ma301987p	journal	February 2013
A novel method for synthesis of styryl phosphonate monoester and its application in La(III) extraction Huang, Kaihua; Jia, Yun; Wang, Shuai Journal of Rare Earths, Vol. 38, Issue 6 https://doi.org/10.1016/j.jre.2019.09.003	journal	June 2020
Acidic organophosphorus extractants—I Extraction of lanthanides by means of dialkyl phosphoric acids—effect of structure and size of alkyl group Kolařík, Z.; Pánková, H. Journal of Inorganic and Nuclear Chemistry, Vol. 28, Issue 10 https://doi.org/10.1016/0022-1902(66)80123-9	journal	October 1966
Relative fission product yields in the USGS TRIGA MARK I reactor Koehl, M. A.; Rundberg, R. S.; Shafer, J. C. Journal of Radioanalytical and Nuclear Chemistry, Vol. 314, Issue 2 https://doi.org/10.1007/s10967-017-5485-6	journal	September 2017
Macrocyclic Ligands with an Unprecedented Size-Selectivity Pattern for the Lanthanide Ions Hu, Aohan; MacMillan, Samantha N.; Wilson, Justin J. Journal of the American Chemical Society, Vol. 142, Issue 31 https://doi.org/10.1021/jacs.0c05217	journal	July 2020
Acidic esters of phosphonic acid as selective extractants for metallic cations-selected M(III) tracer studies Peppard, D. F.; Mason, G. W.; Hucher, I. Journal of Inorganic and Nuclear Chemistry, Vol. 18 https://doi.org/10.1016/0022-1902(61)80394-1	journal	March 1961
A Differential Potentiometric Method of Measuring Acid and Base Dissociation Constants Kilpi, S. Journal of the American Chemical Society, Vol. 74, Issue 21 https://doi.org/10.1021/ja01141a019	journal	November 1952
Photochemical separation of cerium from rare earth mixtures in aqueous solution Donohue, Terence Chemical Physics Letters, Vol. 61, Issue 3 https://doi.org/10.1016/0009-2614(79)87181-X	journal	March 1979
A critical review on solvent extraction of rare earths from aqueous solutions Xie, Feng; Zhang, Ting An; Dreisinger, David Minerals Engineering, Vol. 56 https://doi.org/10.1016/j.mineng.2013.10.021	journal	February 2014
Estimating error limits in parametric curve fitting Caceci, Marco S. Analytical Chemistry, Vol. 61, Issue 20 https://doi.org/10.1021/ac00195a023	journal	October 1989
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide Küchle, W.; Dolg, M.; Stoll, H. The Journal of Chemical Physics, Vol. 100, Issue 10 https://doi.org/10.1063/1.466847	journal	May 1994
Lanthanide photochemistry initiated in f-f transitions Donohue, Terence Journal of the American Chemical Society, Vol. 100, Issue 23 https://doi.org/10.1021/ja00491a048	journal	November 1978
Structural Aspects of Organophosphorus Extractants and Their Metallic Complexes as Deduced from Spectral and Molecular Weight Studies Ferraro, J. R.; Peppard, D. F. Nuclear Science and Engineering, Vol. 16, Issue 4 https://doi.org/10.13182/NSE63-A26550	journal	August 1963
Review: Dissociation, Self-Association, and Partition of Monoacidic Organophosphorus Extractants Kolarik, Z. Solvent Extraction and Ion Exchange, Vol. 28, Issue 6 https://doi.org/10.1080/07366299.2010.515172	journal	October 2010
Pathways for greening the supply of rare earth elements in China Lee, Jason C. K.; Wen, Zongguo Nature Sustainability, Vol. 1, Issue 10 https://doi.org/10.1038/s41893-018-0154-5	journal	October 2018
A molecular basis to rare earth separations for recycling: tuning the TriNOx ligand properties for improved performance Cole, Bren E.; Falcones, Ingemar B.; Cheisson, Thibault Chemical Communications, Vol. 54, Issue 73 https://doi.org/10.1039/C8CC04409K	journal	January 2018
Rare-earth separations enhanced by magnetic field Fan, Bangyu; Li, Fujian; Cheng, Yanyan Separation and Purification Technology, Vol. 301 https://doi.org/10.1016/j.seppur.2022.122025	journal	November 2022
On the Measurement of Buffer Values and on the Relationship of Buffer Value to the Dissociation Constant of the Buffer and the Concentration and Reaction of the Buffer Solution Van Slyke, Donald D. Journal of Biological Chemistry, Vol. 52, Issue 2 https://doi.org/10.1016/S0021-9258(18)85845-8	journal	June 1922
Comparison of some monoacidic organophosphorus esters as lanthanide-actinide extractors and separators Weaver, Boyd; Shoun, R. R. Journal of Inorganic and Nuclear Chemistry, Vol. 33, Issue 6 https://doi.org/10.1016/0022-1902(71)80629-2	journal	June 1971
The Effect of Organic Diluent on the Extraction of Eu(III) by HEH[EHP] Lécrivain, Thibaut; Kimberlin, Ashleigh; E. Dodd, Devon Solvent Extraction and Ion Exchange, Vol. 37, Issue 3-4 https://doi.org/10.1080/07366299.2019.1639371	journal	June 2019
Discrepancies in Solvent Extraction Slope Analysis Caused by Aqueous Buffer Complexation Unger, Aaron J.; Jensen, Mark P. Solvent Extraction and Ion Exchange, Vol. 38, Issue 4 https://doi.org/10.1080/07366299.2020.1750725	journal	April 2020
A set of d-polarization functions for pseudo-potential basis sets of the main group elements AlBi and f-type polarization functions for Zn, Cd, Hg Höllwarth, A.; Böhme, M.; Dapprich, S. Chemical Physics Letters, Vol. 208, Issue 3-4 https://doi.org/10.1016/0009-2614(93)89068-S	journal	June 1993
A Molecular Modelling Study About the Influence of the Structure of Alkyl Chains of Dialkyl Phosphoric Acids on Liquid-Liquid Lanthanide (Iii) Extraction Sella, C.; Nortier, P.; Bauer, D. Solvent Extraction and Ion Exchange, Vol. 15, Issue 6 https://doi.org/10.1080/07366299708934514	journal	November 1997
Analytical-Scale Separations of the Lanthanides: a Review of Techniques and Fundamentals Nash, Kenneth L.; Jensen, Mark P. Separation Science and Technology, Vol. 36, Issue 5-6 https://doi.org/10.1081/SS-100103649	journal	June 2001
Magnetomigration of rare-earth ions in inhomogeneous magnetic fields Franczak, Agnieszka; Binnemans, Koen; Jan Fransaer, Jan Fransaer Physical Chemistry Chemical Physics, Vol. 18, Issue 39 https://doi.org/10.1039/C6CP02575G	journal	January 2016
Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures Bogart, Justin A.; Cole, Bren E.; Boreen, Michael A. Proceedings of the National Academy of Sciences, Vol. 113, Issue 52 https://doi.org/10.1073/pnas.1612628113	journal	December 2016
Recycling of rare earths: a critical review Binnemans, Koen; Jones, Peter Tom; Blanpain, Bart Journal of Cleaner Production, Vol. 51 https://doi.org/10.1016/j.jclepro.2012.12.037	journal	July 2013
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Natural population analysis Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank The Journal of Chemical Physics, Vol. 83, Issue 2 https://doi.org/10.1063/1.449486	journal	July 1985
Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex Picayo, Gabriela A.; Etz, Brian D.; Vyas, Shubham ACS Omega, Vol. 5, Issue 14 https://doi.org/10.1021/acsomega.0c00209	journal	March 2020
Molecular Mechanics Calculations and the Metal Ion Selective Extraction of Lanthanoids Comba, Peter; Gloe, Karsten; Inoue, Katsutoshi Inorganic Chemistry, Vol. 37, Issue 13 https://doi.org/10.1021/ic970673r	journal	June 1998
Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides Jensen, Mark P.; Chiarizia, Renato; Ulicki, Joseph S. Solvent Extraction and Ion Exchange, Vol. 33, Issue 4 https://doi.org/10.1080/07366299.2015.1046292	journal	February 2015
Natural localized molecular orbitals Reed, Alan E.; Weinhold, Frank The Journal of Chemical Physics, Vol. 83, Issue 4 https://doi.org/10.1063/1.449360	journal	August 1985
Synthesis of phosphonates from phenylphosphonic acid and its monoesters Henyecz, Réka; Kiss, Adrienn; Mórocz, Virág Synthetic Communications, Vol. 49, Issue 20 https://doi.org/10.1080/00397911.2019.1637894	journal	July 2019
Natural hybrid orbitals Foster, J. P.; Weinhold, F. Journal of the American Chemical Society, Vol. 102, Issue 24 https://doi.org/10.1021/ja00544a007	journal	September 1980
Interfacial activity of liquid-liquid extraction reagents—I Vandegrift, G. F.; Horwitz, E. P. Journal of Inorganic and Nuclear Chemistry, Vol. 42, Issue 1 https://doi.org/10.1016/0022-1902(80)80056-X	journal	January 1980
Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan Chemical Communications, Vol. 53, Issue 92 https://doi.org/10.1039/C7CC05909D	journal	January 2017
Phosphoryl-Ligand Adducts of Rare Earth-TriNOx Complexes: Systematic Studies and Implications for Separations Chemistry Cheisson, Thibault; Cole, Bren E.; Manor, Brian C. ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 5 https://doi.org/10.1021/acssuschemeng.8b05638	journal	January 2019
Electro-kinetic Separation of Rare Earth Elements Using a Redox-Active Ligand Fang, Huayi; Cole, Bren E.; Qiao, Yusen Angewandte Chemie International Edition, Vol. 56, Issue 43 https://doi.org/10.1002/anie.201706894	journal	September 2017
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 McLean, A. D.; Chandler, G. S. The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648 https://doi.org/10.1063/1.438980	journal	May 1980
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model Barone, Vincenzo; Cossi, Maurizio The Journal of Physical Chemistry A, Vol. 102, Issue 11 https://doi.org/10.1021/jp9716997	journal	March 1998
Acidic esters of orthophosphoric acid as selective extractants for metallic cations—tracer studies Peppard, D. F.; Mason, G. W.; Driscoll, W. J. Journal of Inorganic and Nuclear Chemistry, Vol. 7, Issue 3 https://doi.org/10.1016/0022-1902(58)80078-0	journal	October 1958
Extraction Behaviors of Rare Earth Elements in Solvent Extraction with Single and Mixed Extractant Systems. Extraction of rare earths by phosphoric acid esters containing bulky alkyl groups. II. Ishida, Kyoko; Takeda, Shoji; Takahashi, Toshio Shigen-to-Sozai, Vol. 111, Issue 2 https://doi.org/10.2473/shigentosozai.111.114	journal	January 1995
Purification of Organophosphorus acid Extractants Zhengshui, Hu; Ying, Pan; Wanwu, Ma Solvent Extraction and Ion Exchange, Vol. 13, Issue 5 https://doi.org/10.1080/07366299508918312	journal	August 1995
Photochemical separation of europium from lanthanide mixtures in aqueous solution Donohue, Terence The Journal of Chemical Physics, Vol. 67, Issue 11 https://doi.org/10.1063/1.434656	journal	December 1977
Acidic Phosphinates with Different Alkyl Groups as Extractants for Rare Earths. Hino, Akira; Hirai, Takayuki; Komasawa, Isao JOURNAL OF CHEMICAL ENGINEERING OF JAPAN, Vol. 29, Issue 6 https://doi.org/10.1252/jcej.29.1041	journal	January 1996
Behind the Scenes of Clean Energy: The Environmental Footprint of Rare Earth Products Arshi, Praneet S.; Vahidi, Ehsan; Zhao, Fu ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 3 https://doi.org/10.1021/acssuschemeng.7b03484	journal	January 2018
Magnetic Field Directed Rare‐Earth Separations Higgins, Robert F.; Cheisson, Thibault; Cole, Bren E. Angewandte Chemie International Edition, Vol. 59, Issue 5 https://doi.org/10.1002/anie.201911606	journal	January 2020
Phosphonic Acid Modification of GaInP ₂ Photocathodes Toward Unbiased Photoelectrochemical Water Splitting MacLeod, Bradley A.; Steirer, K. Xerxes; Young, James L. ACS Applied Materials & Interfaces, Vol. 7, Issue 21 https://doi.org/10.1021/acsami.5b01814	journal	May 2015
Solvent Extraction of Metal ions and Separation of Nickel(Ii) from Other Metal ions by Organophosphorus Acids Binghua, Yao; Nagaosa, Yukio; Satake, Masatada Solvent Extraction and Ion Exchange, Vol. 14, Issue 5 https://doi.org/10.1080/07366299608918372	journal	August 1996
Systematic Behavior of Charge-Transfer Transitions and Energy Level Variation in Soft Donor Complexes of the Trivalent Lanthanides Liu, G. K.; Jensen, M. P.; Almond, P. M. The Journal of Physical Chemistry A, Vol. 110, Issue 6 https://doi.org/10.1021/jp0558674	journal	January 2006
Infrared spectral observation on the PO group vibration of some homogeneous series of organic derivatives of P (V) Katzin, Leonard I.; Mason, George W.; Peppard, Donald F. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 34, Issue 1 https://doi.org/10.1016/0584-8539(78)80186-X	journal	January 1978
A Convenient Procedure for the Synthesis of 2,2,2-Trifluoroethyl Methyl 2-Oxoalkylphosphonates Molnár, Katalin; Behra, Julien; Takács, László Phosphorus, Sulfur, and Silicon and the Related Elements, Vol. 190, Issue 5-6 https://doi.org/10.1080/10426507.2014.978326	journal	June 2015
Lanthanide Photocatalysis Qiao, Yusen; Schelter, Eric J. Accounts of Chemical Research, Vol. 51, Issue 11 https://doi.org/10.1021/acs.accounts.8b00336	journal	October 2018
Microwave-assisted direct esterification of cyclic phosphinic acids in the presence of ionic liquids Kiss, Nóra Zsuzsa; Keglevich, György Tetrahedron Letters, Vol. 57, Issue 9 https://doi.org/10.1016/j.tetlet.2016.01.044	journal	March 2016
Redox-Driven Chelation and Kinetic Separation of Select Rare Earths Using a Tripodal Nitroxide Proligand Cole, Bren E.; Cheisson, Thibault; Higgins, Robert F. Inorganic Chemistry https://doi.org/10.1021/acs.inorgchem.9b00975	journal	June 2019
Effect of Changes in Structure of Phosphoric Acid Esters on Extractability of Rare Earths. Extraction of rare earths by phosphoric acid esters containing bulky alkyl groups. I. Takahashi, Toshio; Nishizawa, Hiroaki; Tsuchiya, Yukari Shigen-to-Sozai, Vol. 111, Issue 2 https://doi.org/10.2473/shigentosozai.111.109	journal	January 1995
Derivation of a Generalized Gradient Approximation: The PW91 Density Functional Burke, Kieron; Perdew, John P.; Wang, Yue Electronic Density Functional Theory https://doi.org/10.1007/978-1-4899-0316-7_7	book	January 1998
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann The Journal of Chemical Physics, Vol. 118, Issue 2 https://doi.org/10.1063/1.1521431	journal	January 2003
Advanced liquid–liquid extraction systems for the separation of rare earth ions by combination of conversion of the metal species with chemical reaction Nishihama, Syouhei; Hirai, Takayuki; Komasawa, Isao Journal of Solid State Chemistry, Vol. 171, Issue 1-2 https://doi.org/10.1016/S0022-4596(02)00198-6	journal	February 2003
DCC-assisted direct esterification of phosphinic and phosphoric acids with O-nucleophiles Xiong, Biquan; Wang, Gang; Zhou, Congshan Phosphorus, Sulfur, and Silicon and the Related Elements, Vol. 193, Issue 4 https://doi.org/10.1080/10426507.2017.1395438	journal	November 2017
Molecular Design for Tuning Work Functions of Transparent Conducting Electrodes Koldemir, Unsal; Braid, Jennifer L.; Morgenstern, Amanda The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00420	journal	June 2015
Segmented contraction scheme for small-core actinide pseudopotential basis sets Cao, Xiaoyan; Dolg, Michael Journal of Molecular Structure: THEOCHEM, Vol. 673, Issue 1-3 https://doi.org/10.1016/j.theochem.2003.12.015	journal	March 2004
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni Journal of Computational Chemistry, Vol. 24, Issue 6 https://doi.org/10.1002/jcc.10189	journal	April 2003
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules Hehre, W. J.; Ditchfield, R.; Pople, J. A. The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261 https://doi.org/10.1063/1.1677527	journal	March 1972

Similar Records

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

Journal Article · Fri Oct 27 00:00:00 EDT 2017 · ChemComm · OSTI ID:2006602

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

The Influence of Lactic Acid Concentration on the Separation of Light Rare Earth Elements by Continuous Liquid–Liquid Extraction with 2-Ethylhexyl Phosphonic Acid Mono-2-ethylhexyl Ester

Journal Article · Thu Feb 15 00:00:00 EST 2018 · Metallurgical and Materials Transactions B, Process Metallurgy and Materials Processing Science · OSTI ID:2006602

Carvalho Gomes, Rafael de; Seruff, Luciana Amaral; Scal, Maira Labanca Waineraich

A library of vinyl phosphonate anions dimerize with cyanostars, form supramolecular polymers and undergo statistical sorting

Journal Article · Wed Dec 20 00:00:00 EST 2023 · Chemical Science · OSTI ID:2006602

Chen, Yusheng; Kuvayskaya, Anastasia; Pink, Maren; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
functionalized ligand
lanthanide
rare earth metals
separations

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

Citation Formats

References (66)

Similar Records

Related Subjects