Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent: The role of ion pairs

S. V. Gutorova; D. A. Novichkov; A. L. Trigub; Q. Wang; M. A. Gerasimov; P. Kalle; E. A. Arkhipova; A. S. Ivanov; M. V. Evsiunina; T. R. Poliakova; A. A. Averin; V. G. Petrov; A. V. Khvostov; A. A. Kirsanova; N. E. Borisova; P. I. Matveev

doi:10.1016/j.molliq.2024.126382

Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent: The role of ion pairs

S. V. Gutorova, D. A. Novichkov, A. L. Trigub, Q. Wang, M. A. Gerasimov, P. Kalle, E. A. Arkhipova, A. S. Ivanov, M. V. Evsiunina, T. R. Poliakova, A. A. Averin, V. G. Petrov, A. V. Khvostov, A. A. Kirsanova, N. E. Borisova, P. I. Matveev

Research output: Contribution to journal › Article › peer-review

Abstract

Uranium is a key element in nuclear power. Developing new extraction systems for its purification and concentration is an important task for improving the nuclear fuel cycle. In this work solvent extraction and uranyl complexes with tri-dentate pyridine-based and tetra-dentate phenanthroline-based diphosphonates were studied in thorough detail, both in the organic phase and the solid state. A combination of experimental methods (loading isotherms and conductivity measurements), spectroscopic techniques (UV–vis, EXAFS, ³¹P NMR, and Raman spectroscopy) and theoretical calculations were used to disclose the mechanism of U(VI) solvent extraction. We demonstrated that with tetradentate phenanthroline-based ligands, tight ion pairs ([UO₂LNO₃]⁺[UO₂(NO₃)₃]⁻) are formed. With tridentate ligands, U(VI) forms a mixture of complexes with different stoichiometries. Significant differences in the structure of complexes with tridentate ligands in the solid state compared to complexes in the organic solution were also shown.

Original language	English
Article number	126382
Journal	Journal of Molecular Liquids
Volume	415
DOIs	https://doi.org/10.1016/j.molliq.2024.126382
State	Published - Dec 1 2024
Externally published	Yes

Funding

Synthesis and solvent extraction experiments were supported by RSF project \u211620-73-10076. ICP-MS were carried out on equipment provided by the federal project\u201D Development of infrastructure for scientific research and personnel training\u201D of the national project\u201D Science and Universities\u201D of December 29, 2021 no 15/34. X-ray diffraction studies were performed at the Centre of Shared Equipment of the N.S. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences. A. Trigub acknowledges the Ministry of Science and Higher Education of the Russian Federation for financial support (Agreement \u2116 075-15-2021-1363) for synchrotron studies. Synthesis and solvent extraction experiments were supported by RSF project \u211620-73-10076. A. Trigub acknowledges the Ministry of Science and Higher Education of the Russian Federation for financial support (Agreement \u2116 075-15-2021-1363) for synchrotron studies.

Funders	Funder number
N.S. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences
Russian Science Foundation	20-73-10076, 15/34
Russian Science Foundation
Ministry of Education and Science of the Russian Federation	075-15-2021-1363
Ministry of Education and Science of the Russian Federation

Keywords

EXAFS
Phenanthroline phosphonates
Pyridine phosphonates
Solvent extraction
Uranium

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10.1016/j.molliq.2024.126382

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Gutorova, S. V., Novichkov, D. A., Trigub, A. L., Wang, Q., Gerasimov, M. A., Kalle, P., Arkhipova, E. A., Ivanov, A. S., Evsiunina, M. V., Poliakova, T. R., Averin, A. A., Petrov, V. G., Khvostov, A. V., Kirsanova, A. A., Borisova, N. E., & Matveev, P. I. (2024). Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent: The role of ion pairs. Journal of Molecular Liquids, 415, Article 126382. https://doi.org/10.1016/j.molliq.2024.126382

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title = "Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent: The role of ion pairs",

abstract = "Uranium is a key element in nuclear power. Developing new extraction systems for its purification and concentration is an important task for improving the nuclear fuel cycle. In this work solvent extraction and uranyl complexes with tri-dentate pyridine-based and tetra-dentate phenanthroline-based diphosphonates were studied in thorough detail, both in the organic phase and the solid state. A combination of experimental methods (loading isotherms and conductivity measurements), spectroscopic techniques (UV–vis, EXAFS, 31P NMR, and Raman spectroscopy) and theoretical calculations were used to disclose the mechanism of U(VI) solvent extraction. We demonstrated that with tetradentate phenanthroline-based ligands, tight ion pairs ([UO2LNO3]+[UO2(NO3)3]−) are formed. With tridentate ligands, U(VI) forms a mixture of complexes with different stoichiometries. Significant differences in the structure of complexes with tridentate ligands in the solid state compared to complexes in the organic solution were also shown.",

keywords = "EXAFS, Phenanthroline phosphonates, Pyridine phosphonates, Solvent extraction, Uranium",

author = "Gutorova, {S. V.} and Novichkov, {D. A.} and Trigub, {A. L.} and Q. Wang and Gerasimov, {M. A.} and P. Kalle and Arkhipova, {E. A.} and Ivanov, {A. S.} and Evsiunina, {M. V.} and Poliakova, {T. R.} and Averin, {A. A.} and Petrov, {V. G.} and Khvostov, {A. V.} and Kirsanova, {A. A.} and Borisova, {N. E.} and Matveev, {P. I.}",

note = "Publisher Copyright: {\textcopyright} 2024 Elsevier B.V.",

year = "2024",

month = dec,

day = "1",

doi = "10.1016/j.molliq.2024.126382",

language = "English",

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Gutorova, SV, Novichkov, DA, Trigub, AL, Wang, Q, Gerasimov, MA, Kalle, P, Arkhipova, EA, Ivanov, AS, Evsiunina, MV, Poliakova, TR, Averin, AA, Petrov, VG, Khvostov, AV, Kirsanova, AA, Borisova, NE & Matveev, PI 2024, 'Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent: The role of ion pairs', Journal of Molecular Liquids, vol. 415, 126382. https://doi.org/10.1016/j.molliq.2024.126382

TY - JOUR

T1 - Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent

T2 - The role of ion pairs

AU - Gutorova, S. V.

AU - Novichkov, D. A.

AU - Trigub, A. L.

AU - Wang, Q.

AU - Gerasimov, M. A.

AU - Kalle, P.

AU - Arkhipova, E. A.

AU - Ivanov, A. S.

AU - Evsiunina, M. V.

AU - Poliakova, T. R.

AU - Averin, A. A.

AU - Petrov, V. G.

AU - Khvostov, A. V.

AU - Kirsanova, A. A.

AU - Borisova, N. E.

AU - Matveev, P. I.

PY - 2024/12/1

Y1 - 2024/12/1

N2 - Uranium is a key element in nuclear power. Developing new extraction systems for its purification and concentration is an important task for improving the nuclear fuel cycle. In this work solvent extraction and uranyl complexes with tri-dentate pyridine-based and tetra-dentate phenanthroline-based diphosphonates were studied in thorough detail, both in the organic phase and the solid state. A combination of experimental methods (loading isotherms and conductivity measurements), spectroscopic techniques (UV–vis, EXAFS, 31P NMR, and Raman spectroscopy) and theoretical calculations were used to disclose the mechanism of U(VI) solvent extraction. We demonstrated that with tetradentate phenanthroline-based ligands, tight ion pairs ([UO2LNO3]+[UO2(NO3)3]−) are formed. With tridentate ligands, U(VI) forms a mixture of complexes with different stoichiometries. Significant differences in the structure of complexes with tridentate ligands in the solid state compared to complexes in the organic solution were also shown.

AB - Uranium is a key element in nuclear power. Developing new extraction systems for its purification and concentration is an important task for improving the nuclear fuel cycle. In this work solvent extraction and uranyl complexes with tri-dentate pyridine-based and tetra-dentate phenanthroline-based diphosphonates were studied in thorough detail, both in the organic phase and the solid state. A combination of experimental methods (loading isotherms and conductivity measurements), spectroscopic techniques (UV–vis, EXAFS, 31P NMR, and Raman spectroscopy) and theoretical calculations were used to disclose the mechanism of U(VI) solvent extraction. We demonstrated that with tetradentate phenanthroline-based ligands, tight ion pairs ([UO2LNO3]+[UO2(NO3)3]−) are formed. With tridentate ligands, U(VI) forms a mixture of complexes with different stoichiometries. Significant differences in the structure of complexes with tridentate ligands in the solid state compared to complexes in the organic solution were also shown.

KW - EXAFS

KW - Phenanthroline phosphonates

KW - Pyridine phosphonates

KW - Solvent extraction

KW - Uranium

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U2 - 10.1016/j.molliq.2024.126382

DO - 10.1016/j.molliq.2024.126382

M3 - Article

AN - SCOPUS:85208191186

SN - 0167-7322

VL - 415

JO - Journal of Molecular Liquids

JF - Journal of Molecular Liquids

M1 - 126382

ER -

Disclosing the mechanism of uranium(VI) solvent extraction by polydentate ligands in a polar solvent: The role of ion pairs

Abstract

Funding

Keywords

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