The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials
Abstract
Industrial rare earth element (REE) separations predominantly utilize solvent extraction processes tailored toward conventional resources such as bastnäsite, monazite, and ion adsorption clays. Advances in diglycolamide (DGA) chemistry have shown effective extraction characteristics for REE separations. However, limitations associated with traditional DGA solvent extraction techniques, such as third-phase formation and gelling, have hindered commercial viability. By supporting DGA extractants on porous resins such as polystyrene divinyl benzene (PS-DVB), the desirable combination of solvent extraction selectivity and ease of operation of sorbent columns can be achieved. To design a low-cost model for such solid-supported DGAs, extraction characteristics as influenced by the underlying coordination chemistry must be explored to achieve efficient functional systems. Within this study, we report novel DGA resin materials, each incorporating one of the DGAs N,N,N’,N’-tetra-(1-octyl)-3-oxapentane-1,5-diamide (TODGA), N,N'-dimethyl-N,N'-dioctyl-3-oxapentane-1,5-diamide (DMDODGA), and 2,2'-oxybis(1-(3-(((2-ethylhexyl)thio)methyl)-4-methylpyrrolidin-1-yl)ethan-1-one) (DEHPDGA). The affinity of DGAs across the lanthanide (Ln) series was evaluated for both hydrochloric acid and nitric acid media with varying Ln feed concentrations to study distribution ratios and loading characteristics. Focusing on dysprosium, extended X-Ray Absorption Fine Structure (EXAFS) and density functional theory (DFT) calculations were also utilized to explore coordination chemistry and their effects on ligand performance. Further, the general trend for both acid mediamore »
- Authors:
-
[2];
[3];
[3];
[5];
[3];
[3]
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); SHINE Medical Technologies, LLC, Janesville, WI (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chevron, Energy Technology Company, Houston, TX (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1831687
- Alternate Identifier(s):
- OSTI ID: 1871332; OSTI ID: 1958992
- Report Number(s):
- INL/JOU-20-60271-Rev000
Journal ID: ISSN 0736-6299
- Grant/Contract Number:
- AC05-00OR22725; AC02-06CH11357; AC02-05CH11231; AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Solvent Extraction and Ion Exchange
- Additional Journal Information:
- Journal Volume: 40; Journal Issue: 1-2; Journal ID: ISSN 0736-6299
- Publisher:
- Taylor and Francis
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; diglycolamide; extraction chromatography; rare earth separations; 42 ENGINEERING; Rare Earth Elements; Extended X-Ray Absorption Fine Structure (EXAFS)
Citation Formats
Flores, Ramedy, Momen, Abdul, Healy, Mary, Jansone-Popova, Santa, Lyon, Kevin, Reinhart, Benjamin, Cheshire, Michael C., Moyer, Bruce A., and Bryantsev, Vyacheslav. The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials. United States: N. p., 2021.
Web. doi:10.1080/07366299.2021.1956121.
Flores, Ramedy, Momen, Abdul, Healy, Mary, Jansone-Popova, Santa, Lyon, Kevin, Reinhart, Benjamin, Cheshire, Michael C., Moyer, Bruce A., & Bryantsev, Vyacheslav. The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials. United States. https://doi.org/10.1080/07366299.2021.1956121
Flores, Ramedy, Momen, Abdul, Healy, Mary, Jansone-Popova, Santa, Lyon, Kevin, Reinhart, Benjamin, Cheshire, Michael C., Moyer, Bruce A., and Bryantsev, Vyacheslav. Mon .
"The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials". United States. https://doi.org/10.1080/07366299.2021.1956121. https://www.osti.gov/servlets/purl/1831687.
@article{osti_1831687,
title = {The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials},
author = {Flores, Ramedy and Momen, Abdul and Healy, Mary and Jansone-Popova, Santa and Lyon, Kevin and Reinhart, Benjamin and Cheshire, Michael C. and Moyer, Bruce A. and Bryantsev, Vyacheslav},
abstractNote = {Industrial rare earth element (REE) separations predominantly utilize solvent extraction processes tailored toward conventional resources such as bastnäsite, monazite, and ion adsorption clays. Advances in diglycolamide (DGA) chemistry have shown effective extraction characteristics for REE separations. However, limitations associated with traditional DGA solvent extraction techniques, such as third-phase formation and gelling, have hindered commercial viability. By supporting DGA extractants on porous resins such as polystyrene divinyl benzene (PS-DVB), the desirable combination of solvent extraction selectivity and ease of operation of sorbent columns can be achieved. To design a low-cost model for such solid-supported DGAs, extraction characteristics as influenced by the underlying coordination chemistry must be explored to achieve efficient functional systems. Within this study, we report novel DGA resin materials, each incorporating one of the DGAs N,N,N’,N’-tetra-(1-octyl)-3-oxapentane-1,5-diamide (TODGA), N,N'-dimethyl-N,N'-dioctyl-3-oxapentane-1,5-diamide (DMDODGA), and 2,2'-oxybis(1-(3-(((2-ethylhexyl)thio)methyl)-4-methylpyrrolidin-1-yl)ethan-1-one) (DEHPDGA). The affinity of DGAs across the lanthanide (Ln) series was evaluated for both hydrochloric acid and nitric acid media with varying Ln feed concentrations to study distribution ratios and loading characteristics. Focusing on dysprosium, extended X-Ray Absorption Fine Structure (EXAFS) and density functional theory (DFT) calculations were also utilized to explore coordination chemistry and their effects on ligand performance. Further, the general trend for both acid media resulted in DMDODGA having the highest extraction strength of all three DGAs at varying acid concentrations. Coordination-chemistry analysis supported by loading data, DFT calculations, and EXAFS results under forced loading conditions posited less than the expected 3:1 ligand-to-metal coordination.},
doi = {10.1080/07366299.2021.1956121},
journal = {Solvent Extraction and Ion Exchange},
number = 1-2,
volume = 40,
place = {United States},
year = {Mon Sep 06 00:00:00 EDT 2021},
month = {Mon Sep 06 00:00:00 EDT 2021}
}
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
An europium( iii ) diglycolamide complex: insights into the coordination chemistry of lanthanides in solvent extraction
journal, January 2015
- Antonio, Mark R.; McAlister, Daniel R.; Horwitz, E. Philip
- Dalton Transactions, Vol. 44, Issue 2
A fluorescence study on the complexation of Sm( iii ), Eu( iii ) and Tb( iii ) with tetraalkyldiglycolamides (TRDGA) in aqueous solution, in solid state, and in solvent extraction
journal, January 2016
- Kou, Fei; Yang, Suliang; Qian, Hongjuan
- Dalton Transactions, Vol. 45, Issue 46
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 78, Issue 7
Extraction Chromatographic Materials for Clean Hydrometallurgical Separation of Rare-Earth Elements Using Diglycolamide Extractants
journal, October 2019
- Momen, M. A.; Healy, M. R.; Tsouris, C.
- Industrial & Engineering Chemistry Research, Vol. 58, Issue 43
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Aqueous Partitioning of Minor Actinides by Different Processes
journal, February 2011
- Ansari, Seraj A.; Pathak, Priyanath; Mohapatra, Prashanta K.
- Separation & Purification Reviews, Vol. 40, Issue 1
Seven chemical separations to change the world
journal, April 2016
- Sholl, David S.; Lively, Ryan P.
- Nature, Vol. 532, Issue 7600
Role of alkyl chain branching on aggregation behavior of two symmetrical diglycolamides: Small angle neutron scattering studies
journal, March 2013
- Pathak, P. N.; Ansari, S. A.; Mohapatra, P. K.
- Journal of Colloid and Interface Science, Vol. 393
Simulated moving bed technology: old and new
journal, September 2006
- Sá Gomes, Pedro; Minceva, Mirjana; Rodrigues, Alírio E.
- Adsorption, Vol. 12, Issue 5-6
Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides
journal, June 2018
- Baldwin, Anna G.; Ivanov, Alexander S.; Williams, Neil J.
- ACS Central Science, Vol. 4, Issue 6
Ligand-assisted elution chromatography for separation of lanthanides
journal, April 2015
- Ling, Lei; Wang, Nien-Hwa Linda
- Journal of Chromatography A, Vol. 1389
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
A critical review on solvent extraction of rare earths from aqueous solutions
journal, February 2014
- Xie, Feng; Zhang, Ting An; Dreisinger, David
- Minerals Engineering, Vol. 56
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Reverse-Micelle Formation in the Partitioning of Trivalent f-Element Cations by Biphasic Systems Containing a Tetraalkyldiglycolamide
journal, April 2007
- Jensen, Mark P.; Yaita, Tsuyoshi; Chiarizia, Renato
- Langmuir, Vol. 23, Issue 9
A SAXS Study of Aggregation in the Synergistic TBP–HDBP Solvent Extraction System
journal, May 2013
- Ellis, Ross J.; Anderson, Timothy L.; Antonio, Mark R.
- The Journal of Physical Chemistry B, Vol. 117, Issue 19
Insight into the Complexation of Actinides and Lanthanides with Diglycolamide Derivatives: Experimental and Density Functional Theoretical Studies
journal, March 2017
- Sengupta, Arijit; Bhattacharyya, Arunasis; Verboom, Willem
- The Journal of Physical Chemistry B, Vol. 121, Issue 12
Adsorption and chromatographic separation of rare earths with EDTA- and DTPA-functionalized chitosan biopolymers
journal, January 2014
- Roosen, Joris; Binnemans, Koen
- J. Mater. Chem. A, Vol. 2, Issue 5
Understanding Lanthanoid(III) Hydration Structure and Kinetics by Insights from Energies and Wave functions
journal, June 2014
- Zhang, Jun; Heinz, Norah; Dolg, Michael
- Inorganic Chemistry, Vol. 53, Issue 14
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Crystal Structures of Lanthanoid(III) (Ln(III), Ln = Tb, Dy, Ho, Er, Tm, Yb, and Lu) Nitrate Complexes with N , N , N ′, N ′-Tetraethyldiglycolamide
journal, October 2014
- Okumura, Shin; Kawasaki, Takeshi; Sasaki, Yuji
- Bulletin of the Chemical Society of Japan, Vol. 87, Issue 10
Trefoil-Shaped Outer-Sphere Ion Clusters Mediate Lanthanide(III) Ion Transport with Diglycolamide Ligands
journal, November 2017
- Brigham, Derek M.; Ivanov, Alexander S.; Moyer, Bruce A.
- Journal of the American Chemical Society, Vol. 139, Issue 48
The Effect of Alkyl Substituents on Actinide and Lanthanide Extraction by Diglycolamide Compounds
journal, August 2015
- Sasaki, Yuji; Sugo, Yumi; Morita, Keisuke
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 7
“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands
journal, November 2016
- Ellis, Ross J.; Brigham, Derek M.; Delmau, Laetitia
- Inorganic Chemistry, Vol. 56, Issue 3
Rare earth elements: Mendeleev’s bane, modern marvels
journal, January 2019
- Cheisson, Thibault; Schelter, Eric J.
- Science, Vol. 363, Issue 6426
Criticality of the Rare Earth Elements: Criticality of the Rare Earth Elements
journal, March 2015
- Nassar, N. T.; Du, Xiaoyue; Graedel, T. E.
- Journal of Industrial Ecology, Vol. 19, Issue 6
Application and Comparison of High-Speed Countercurrent Chromatography and High Performance Liquid Chromatography in Preparative Enantioseparation of α -Substitution Mandelic Acids
journal, October 2014
- Tong, Shengqiang; Zhang, Hu; Shen, Mangmang
- Separation Science and Technology, Vol. 50, Issue 5
Hydration of Lanthanoid(III) Ions in Aqueous Solution and Crystalline Hydrates Studied by EXAFS Spectroscopy and Crystallography: The Myth of the “Gadolinium Break”
journal, March 2008
- Persson, Ingmar; D'Angelo, Paola; De Panfilis, Simone
- Chemistry - A European Journal, Vol. 14, Issue 10
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Uncovering the end uses of the rare earth elements
journal, September 2013
- Du, Xiaoyue; Graedel, T. E.
- Science of The Total Environment, Vol. 461-462