Solvent Extraction and Ion Exchange, volume 32, issue 5, pages 508-528

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Publication typeJournal Article
Publication date2014-06-06
Quartile SCImago
Q2
Quartile WOS
Q3
Impact factor2
ISSN07366299, 15322262
General Chemistry
General Chemical Engineering
Abstract
This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln3+) and 5f-elements (actinides, An3+) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln3+ and An3+ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu3+/Am3+ model pair cations (SFAm/Eu) in extraction experiments on a semi-quantitative level. The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM]3+, (H2O)nM(NO3)3 (n = 3, 4), and LM(NO3)3 (M = Eu, Am). Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln3+ and An3+ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An3+ and Ln3+ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation. Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N′,N′-tetraalkyl diamides (“effect of anomalous aryl strengthening”). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An3+/Ln3separation selectivity in the series of dipicolinic acid diamides.

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Ustynyuk Y. A. et al. Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study // Solvent Extraction and Ion Exchange. 2014. Vol. 32. No. 5. pp. 508-528.
GOST all authors (up to 50) Copy
Ustynyuk Y. A., Gloriozov I. P., Kalmykov S. N., Mitrofanov A. A., Babain V. A., Alyapyshev M. Yu., Ustynyuk N. A., Kalmykov S. N., Alyapyshev M. Yu. Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study // Solvent Extraction and Ion Exchange. 2014. Vol. 32. No. 5. pp. 508-528.
RIS |
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RIS Copy
TY - JOUR
DO - 10.1080/07366299.2014.915666
UR - https://doi.org/10.1080%2F07366299.2014.915666
TI - Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study
T2 - Solvent Extraction and Ion Exchange
AU - Ustynyuk, Yuri A.
AU - Gloriozov, Igor P.
AU - Kalmykov, Stepan N.
AU - Mitrofanov, Artyom A
AU - Babain, Vassily A
AU - Alyapyshev, Mikhail Yu
AU - Ustynyuk, Nickolay A
AU - Kalmykov, Stepan N.
AU - Alyapyshev, M Yu
PY - 2014
DA - 2014/06/06 00:00:00
PB - Taylor & Francis
SP - 508-528
IS - 5
VL - 32
SN - 0736-6299
SN - 1532-2262
ER -
BibTex |
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@article{2014_Ustynyuk
author = {Yuri A. Ustynyuk and Igor P. Gloriozov and Stepan N. Kalmykov and Artyom A Mitrofanov and Vassily A Babain and Mikhail Yu Alyapyshev and Nickolay A Ustynyuk and Stepan N. Kalmykov and M Yu Alyapyshev},
title = {Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study},
journal = {Solvent Extraction and Ion Exchange},
year = {2014},
volume = {32},
publisher = {Taylor & Francis},
month = {jun},
url = {https://doi.org/10.1080%2F07366299.2014.915666},
number = {5},
pages = {508--528},
doi = {10.1080/07366299.2014.915666}
}
MLA
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Ustynyuk, Yuri A., et al. “Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study.” Solvent Extraction and Ion Exchange, vol. 32, no. 5, Jun. 2014, pp. 508-528. https://doi.org/10.1080%2F07366299.2014.915666.
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