Efficient Separation of Light Lanthanides(III) by Using Bis-Lactam Phenanthroline Ligands

Healy, Mary R.; Ivanov, Aleksandr; Isaichykava, Yana A.; Bryantsev, Vyacheslav; Moyer, Bruce A.; Jansone-Popova, Santa

doi:10.1002/chem.201806443

Title: Efficient Separation of Light Lanthanides(III) by Using Bis-Lactam Phenanthroline Ligands

Journal Article · 24 February 2019 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201806443 · OSTI ID:1526392

^[1];

^[1]; Isaichykava, Yana A. ^[1];

^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Furthermore, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1526392

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 25 Vol. 25; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (38)

Quantum Mechanical Continuum Solvation Models Tomasi, Jacopo; Menucci, Benedetta; Cammi, Roberto ChemInform, Vol. 36, Issue 42 https://doi.org/10.1002/chin.200542292	journal	October 2005
A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides: A Computational Approach to Predicting Ligand Selectivity for the Size-Based Separation of Trivalent Lanthanides Ivanov, Alexander S.; Bryantsev, Vyacheslav S. European Journal of Inorganic Chemistry, Vol. 2016, Issue 21 https://doi.org/10.1002/ejic.201600319	journal	June 2016
Development and validation of COMPASS force field parameters for molecules with aliphatic azide chains McQuaid, Michael J.; Sun, Huai; Rigby, David Journal of Computational Chemistry, Vol. 25, Issue 1 https://doi.org/10.1002/jcc.10316	journal	January 2003
Energy-adjusted pseudopotentials for the rare earth elements Dolg, M.; Stoll, H.; Savin, A. Theoretica Chimica Acta, Vol. 75, Issue 3 https://doi.org/10.1007/BF00528565	journal	January 1989
Solvent extraction of lanthanoid/III/ with 18-crown-6 from aqueous trichloroacetate solutions to 1,2-dichloroethane Samy, T. M.; Imura, H.; Suzuki, N. Journal of Radioanalytical and Nuclear Chemistry Letters, Vol. 126, Issue 2 https://doi.org/10.1007/BF02162434	journal	January 1988
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Liquid-liquid extraction of rare-earth elements from aqueous acid solutions by acid organophosphorus compounds Sato, Taichi Hydrometallurgy, Vol. 22, Issue 1-2 https://doi.org/10.1016/0304-386X(89)90045-5	journal	June 1989
On the stability of palladium(II) aquo complexes with 2,2′-bipyridyl and 1,10-phenanthroline Wimmer, Franz L.; Wimmer, Smita Inorganica Chimica Acta, Vol. 149, Issue 1 https://doi.org/10.1016/S0020-1693(00)90558-9	journal	September 1988
2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)-pyridine: Structures of An(III) and Ln(III) 1:3 complexes and selectivity Banik, Nidhu L.; Denecke, Melissa A.; Geist, Andreas Inorganic Chemistry Communications, Vol. 29 https://doi.org/10.1016/j.inoche.2012.11.032	journal	March 2013
The novel extraction process based on CYANEX® 572 for separating heavy rare earths from ion-adsorbed deposit Wang, Yanliang; Li, Fujian; Zhao, Zeyuan Separation and Purification Technology, Vol. 151 https://doi.org/10.1016/j.seppur.2015.07.063	journal	September 2015
Preorganization of diglycolamides on the calix[4]arene platform and its effect on the extraction of Am(III)/Eu(III) Iqbal, Mudassir; Mohapatra, Prasanta K.; Ansari, Seraj A. Tetrahedron, Vol. 68, Issue 38 https://doi.org/10.1016/j.tet.2012.07.036	journal	September 2012
Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency Jansone-Popova, Santa; Ivanov, Alexander S.; Bryantsev, Vyacheslav S. Inorganic Chemistry, Vol. 56, Issue 10 https://doi.org/10.1021/acs.inorgchem.7b00555	journal	April 2017
Chemistry of Diglycolamides: Promising Extractants for Actinide Partitioning Ansari, Seraj A.; Pathak, Priyanath; Mohapatra, Prasanta K. Chemical Reviews, Vol. 112, Issue 3 https://doi.org/10.1021/cr200002f	journal	November 2011
Quantum Mechanical Continuum Solvation Models Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto Chemical Reviews, Vol. 105, Issue 8 https://doi.org/10.1021/cr9904009	journal	August 2005
Trivalent Actinide and Lanthanide Separations by Tetradentate Nitrogen Ligands: A Quantum Chemistry Study Lan, Jian-Hui; Shi, Wei-Qun; Yuan, Li-Yong Inorganic Chemistry, Vol. 50, Issue 19 https://doi.org/10.1021/ic200078j	journal	October 2011
Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides Hudson, Michael J.; Harwood, Laurence M.; Laventine, Dominic M. Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3008848	journal	June 2012
Deliberate Design of Ligand Architecture Yields Dramatic Enhancement of Metal Ion Affinity Lumetta, Gregg J.; Rapko, Brian M.; Garza, Priscilla A. Journal of the American Chemical Society, Vol. 124, Issue 20 https://doi.org/10.1021/ja025854t	journal	May 2002
Highly Efficient Separation of Actinides from Lanthanides by a Phenanthroline-Derived Bis-triazine Ligand Lewis, Frank W.; Harwood, Laurence M.; Hudson, Michael J. Journal of the American Chemical Society, Vol. 133, Issue 33 https://doi.org/10.1021/ja203378m	journal	August 2011
Use of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation Ribeiro, Raphael F.; Marenich, Aleksandr V.; Cramer, Christopher J. The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp205508z	journal	December 2011
A supramolecular lanthanide separation approach based on multivalent cooperative enhancement of metal ion selectivity Li, Xiao-Zhen; Zhou, Li-Peng; Yan, Liang-Liang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02940-7	journal	February 2018
Multicoordinate ligands for actinide/lanthanide separations Dam, Henk H.; Reinhoudt, David N.; Verboom, Willem Chem. Soc. Rev., Vol. 36, Issue 2 https://doi.org/10.1039/B603847F	journal	January 2007
Challenges to achievement of metal sustainability in our high-tech society Izatt, Reed M.; Izatt, Steven R.; Bruening, Ronald L. Chem. Soc. Rev., Vol. 43, Issue 8 https://doi.org/10.1039/C3CS60440C	journal	January 2014
N,N′-Dialkyl-N,N′-diaryl-1,10-phenanthroline-2,9-dicarboxamides as donor ligands for separation of rare earth elements with a high and unusual selectivity. DFT computational and experimental studies Ustynyuk, Yu. A.; Borisova, N. E.; Babain, V. A. Chemical Communications, Vol. 51, Issue 35 https://doi.org/10.1039/C5CC01620G	journal	January 2015
Separation and complexation of palladium( ii ) with a new soft N-donor ligand 6,6′-bis(5,6-dinonyl-1,2,4-triazin-3-yl)-2,2′-bipyridine (C9-BTBP) in nitric acid medium Zhang, Anyun; Xu, Lei; Lei, Gaoming New Journal of Chemistry, Vol. 40, Issue 7 https://doi.org/10.1039/C5NJ03082J	journal	January 2016
Selective separation of trivalent f-ions using 1,10-phenanthroline-2,9-dicarboxamide ligands in ionic liquids Dehaudt, Jérémy; Williams, Neil J.; Shkrob, Ilya A. Dalton Transactions, Vol. 45, Issue 29 https://doi.org/10.1039/C6DT01800A	journal	January 2016
Exploring electronic effects on the partitioning of actinides( iii ) from lanthanides( iii ) using functionalised bis-triazinyl phenanthroline ligands Edwards, Alyn C.; Wagner, Christoph; Geist, Andreas Dalton Transactions, Vol. 45, Issue 45 https://doi.org/10.1039/C6DT02474B	journal	January 2016
Ligands for f-element extraction used in the nuclear fuel cycle Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem Chemical Society Reviews, Vol. 46, Issue 23 https://doi.org/10.1039/C7CS00574A	journal	January 2017
A novel highly selective ligand for separation of actinides and lanthanides in the nuclear fuel cycle. Experimental verification of the theoretical prediction Lavrov, H. V.; Ustynyuk, N. A.; Matveev, P. I. Dalton Transactions, Vol. 46, Issue 33 https://doi.org/10.1039/C7DT01009E	journal	January 2017
Challenges to achievement of metal sustainability in our high-tech society Izatt, Reed M.; Izatt, Steven R.; Bruening, Ronald L. Chem. Soc. Rev., Vol. 43, Issue 8 https://doi.org/10.1039/c3cs60440c	journal	January 2014
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
Quantum chemical modelling of extraction separation of minor actinides and lanthanides: the state of the art Ustynyuk, Yu A.; Alyapyshev, M. Yu; Babain, V. A. Russian Chemical Reviews, Vol. 85, Issue 9 https://doi.org/10.1070/RCR4588	journal	September 2016
Direct Selective Extraction of Trivalent Americium from PUREX Raffinate Using a Combination of CyMe ₄ BTPhen and TEDGA—A Feasibility Study Lange, Steve; Wilden, Andreas; Modolo, Giuseppe Solvent Extraction and Ion Exchange, Vol. 35, Issue 3 https://doi.org/10.1080/07366299.2017.1326761	journal	March 2017
Cyanex 923 as an Extractant for Trivalent Lanthanides and Yttrium Reddy, M. L. P.; Luxmi Varma, R.; Ramamohan, T. R. Solvent Extraction and Ion Exchange, Vol. 16, Issue 3 https://doi.org/10.1080/07366299808934553	journal	May 1998
THE NOVEL EXTRACTANTS, DIGLYCOLAMIDES, FOR THE EXTRACTION OF LANTHANIDES AND ACTINIDES IN HNO ₃ – n -DODECANE SYSTEM Sasaki, Yuji; Sugo, Yumi; Suzuki, Shinichi Solvent Extraction and Ion Exchange, Vol. 19, Issue 1 https://doi.org/10.1081/SEI-100001376	journal	January 2001
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Metal ion selectivities of the highly preorganized tetradentate ligand 1,10-phenanthroline-2,9-dicarboxamide with lanthanide(III) ions and some actinide ions Merrill, Danielle; Hancock, Robert D. Radiochimica Acta, Vol. 99, Issue 3 https://doi.org/10.1524/ract.2011.1805	journal	March 2011
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Robert, Parr,; Chengteh, Lee,; Weitao, Yang, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/zrp0-ry04	text	January 1988
U.S. Department of Energy Critical Materials Strategy Bauer, D.; Diamond, D.; Li, J. https://doi.org/10.2172/1000846	report	December 2010

Cited By (3)

Magnetic Field Directed Rare‐Earth Separations Higgins, Robert F.; Cheisson, Thibault; Cole, Bren E. Angewandte Chemie, Vol. 132, Issue 5 https://doi.org/10.1002/ange.201911606	journal	December 2019
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
Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent Karslyan, Yana; Sloop, Frederick V.; Delmau, Laetitia H. RSC Advances, Vol. 9, Issue 46 https://doi.org/10.1039/c9ra06115k	journal	January 2019

Similar Records

Bis-lactam-1,10-phenanthroline (BLPhen), a New Type of Preorganized Mixed N,O-Donor Ligand That Separates Am(III) over Eu(III) with Exceptionally High Efficiency

Journal Article · 2017 · Inorganic Chemistry · OSTI ID:1356918

Jansone-Popova, Santa; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; +5 more

Sequestration of trivalent americium and lanthanide nitrates with bis-lactam-1,10-phenanthroline ligand in a hydrocarbon solvent

Journal Article · 2018 · RSC Advances · OSTI ID:1558683

Karslyan, Yana; Sloop, Frederick V.; Delmau, Laetitia H.; +4 more

Changes in nitrate binding with lanthanides in BLPhen complexes

Journal Article · 2023 · Journal of Molecular Liquids · OSTI ID:1995657

Reddy, Th. Dhileep N.; Ivanov, Alexander S.; Driscoll, Darren M.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
N ligands
biphasic separation
lanthanides
nitrogen heterocycles
transition metals

Title: Efficient Separation of Light Lanthanides(III) by Using Bis-Lactam Phenanthroline Ligands

Citation Formats

References (38)

Cited By (3)

Similar Records

Related Subjects