Isolation and Purification of Actinides Using N,O-Hybrid Donor Ligands for Closing the Nuclear Fuel Cycle

Alyapyshev, M. Yu.; Бабаин, В. А.; Kirsanov, Dmitry

doi:10.3390/en15197380

Cited by 21 publications

(9 citation statements)

References 178 publications

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“…The past decade has witnessed a flourishing development of actinide/lanthanide complexation and separation by employing N,O-hybrid ligands based on rigid N-heterocyclic skeletons. − Shi et al reported a tetradentate N,O-hybrid ligand, N , N ′-diethyl- N , N ′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), with well-preorganized amide oxygen and nitrogen atoms, which exhibits good extraction ability and selectivity toward actinides over lanthanides . More recently, Zabierowski et al reported that 2,2′-bipyrimidine-4,4′-dicarboxylic acid could bind to lanthanides to form stable complexes, in which the pyrimidine nitrogen atoms and carboxylic oxygen atoms involved in coordination on the same molecule always lie approximately in the same plane.…”

Section: Introductionmentioning

confidence: 99%

Selective Complexation and Separation of Uranium(VI) from Thorium(IV) with New Tetradentate N,O-Hybrid Diamide Ligands: Synthesis, Extraction, Spectroscopy, and Crystallographic Studies

Wang

Yang

et al. 2023

Inorg. Chem.

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An unmet challenge in the thorium-uranium fuel cycle is the efficient separation of uranium from thorium. Herein, two new tetradentate N,O-hybrid ligands, N,N′-diethyl-N,N′-di-p-tolyl-2,2′-bipyridine-6,6′-dicarboxamide (Et-Tol-BPDA) and N,N′-diethyl-N,N′-di-p-tolyl-2,2′-bipyrimidine-4,4′-dicarboxamide (Et-Tol-BPymDA), comprising a bipyridine or bipyrimidine core and amide moieties were designed and synthesized for selectively complexing and separating U(VI) from Th(IV). The high U(VI)/ Th(IV) extraction selectivity was achieved by Et-Tol-BPDA (SF U/Th = 33 at 3 M HNO 3 ) and Et-Tol-BPymDA (SF U/Th = 73 at 3 M HNO 3 ) in nitric acid solutions. The extraction process for U(VI) or Th(IV) with these two ligands primarily proceeded through the solvation mechanism, as evidenced by slope analyses. Thermodynamic studies for the extraction of U(VI) and Th(IV) revealed a spontaneous process. Results from UV−vis spectroscopic titration and slope analyses demonstrated that U(VI) and Th(IV) each form a 1:1 complex with the two ligands both in the monophasic organic solution and the biphasic extraction system. The stability constants of the 1:1 complexes of Et-Tol-BPDA or Et-Tol-BPymDA with U(VI) were found to be larger than those with Th(IV), which coincide well with the high U(VI)/Th(IV) extraction selectivity. The solid-state structures of Et-Tol-BPDA, Et-Tol-BPymDA, and 1:1 complexes of the two ligands with U(VI) or Th(IV) were analyzed by X-ray diffraction technique. The results from this work implicate the potential of bipyridine-and bipyrimidinederived diamide ligands for uranium/thorium separation.

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Section: Introductionmentioning

confidence: 99%

Selective Complexation and Separation of Uranium(VI) from Thorium(IV) with New Tetradentate N,O-Hybrid Diamide Ligands: Synthesis, Extraction, Spectroscopy, and Crystallographic Studies

Wang

Yang

et al. 2023

Inorg. Chem.

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“…The extractants containing the highly preorganized phenanthroline skeleton exhibit outstanding advantages such as high extraction efficiency, fast kinetics, and strong acid resistance, which have been applied to the group separation of actinides over lanthanides from acidic solutions. – The novel tetradentate ligand N , N ′-diethyl- N , N ′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) (Figure d) reported by Xiao et al exhibited strong extraction ability toward actinides with different oxidation states ( D Th(IV) = 205, D U(VI) = 25, and D Am(III) = 6, 1 M HNO 3 ). By tailoring the substitute groups in the diamide moieties, a series of ligands were synthesized and applied to the actinide extraction.…”

Section: Introductionmentioning

confidence: 99%

Selective Extraction of Uranium(VI) from Thorium(IV) Using New Unsymmetrical Acidic Phenanthroline Carboxamide Ligands

Wang,

Yang,

et al. 2023

Ind. Eng. Chem. Res.

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In the thorium−uranium fuel cycle, 232 Th will produce fissional 233 U and radioactive 232 U simultaneously after irradiation. The selective separation of uranium from thorium-based spent fuel can enhance the utilization efficiency of nuclear fuel and promote the safety of nuclear energy utilization. In this work, a new type of unsymmetrical acidic phenanthroline carboxamide ligand represented as 9-(N,N-dialkylcarbamoyl)-1,10-phenanthroline-2-carboxylic acid (DEAPA and DOAPA) was synthesized for selective separation of U(VI) over Th(IV). The separation of small amounts of U(VI) from large amounts of Th(IV) could be achieved by using DOAPA to extract at high acidity (4 M HNO 3 ) and then using 1 M HNO 3 as the stripping agent. The complexation mechanism of these two ligands with U(VI) and Th(IV) was investigated through slope analysis, NMR spectrometric titration, UV−vis spectrophotometric titration, and single-crystal Xray diffraction methods. Results from slope analysis and NMR spectrometric titration showed that DOAPA formed a 1:1 complex with U(VI) and formed 1:1 and 1:2 complexes with Th(IV). The larger stability constants (log β) of 1:1 complexes of DEAPA/DOAPA with U(VI) than those with Th(IV) implied the stronger affinity of the ligands with U(VI), which was in good coincidence with the solvent extraction results. The crystal structures of the 1:1 complex of U(VI) and the two species of 1:1 and 1:2 complexes of Th(IV) with DEAPA were successfully analyzed by X-ray diffraction. This work provided a new type of unsymmetrical acidic phenanthroline carboxamide extractant for the efficient separation of U(VI) from Th(IV). The systematic study of the extraction and complexation behavior would be helpful to explore the effect of functional groups as well as design extractants with excellent performance.

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“…Nowadays, there is a significant interest in 1,10-phenanthroline ligands as nitrogen-containing building blocks for coordination and organometallic chemistry. , These ligands have functionalized substituents that enhance their efficiency in separating f-elements. − Additionally, the presence of chiral centers in these ligands allows for asymmetric complex catalysis. − Half-sandwich Ru(II), Ir(III), and Rh(III) complexes with substituted 1,10-phenanthrolines have been proven to be highly effective catalysts. − Furthermore, Ru(II) complexes of substituted phenanthrolines have shown potential in treating brain cancer. , Copper(II) and nickel(II) complexes with asymmetric phenanthroline derivatives have also been extensively studied. − Unsymmetrical 1,10-phenanthrolines have been identified as promising ligands for Ru(II) complexes to act as photosensitizers in solar cells . Moreover, a Ru-complex of 4,7-diaminosubstituted 1,10-phenanthroline has been reported to be useful for selective dual-channel detection of Cu(II) ions .…”

Section: Introductionmentioning

confidence: 99%

4-Oxo-7-fluoro-1,10-phenanthroline-2,9-diamides: Synthesis, Structural Features, Lanthanide Complexes, and Am(III)/Ln(III) Solvent Extraction

Avagyan,

Lemport,

Roznyatovsky

et al. 2023

Inorg. Chem.

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A highly efficient synthetic approach was developed for the synthesis of unsymmetrical 1,10-phenanthroline-2,9-diamides with two different substituents in the fourth and seventh positions of the phenanthroline core. The structures of these ligands were confirmed using various spectral methods including 2D-NMR and X-ray analysis. Quantum chemical calculations supported the presence of tautomeric forms of these ligands. Furthermore, it was discovered that these compounds exhibit polydentate ligand behavior toward lanthanide nitrates. The structural characteristics of the complexes formed between these ligands and lanthanide nitrates were investigated both in the solid state and in solution. To further understand the binding properties of these novel unsymmetrical ligands, the binding constants for potential complexes were quantitatively measured by using UV–vis spectrophotometric titration. This allowed for a comprehensive analysis of the binding affinity and stability of these complexes. Extraction experiments of f-elements were performed for symmetrical and unsymmetrical diamides. Overall, this study presents significant advancement in the synthesis and characterization of unsymmetrical 1,10-phenanthroline-2,9-diamides and provides valuable insights into their potential applications as polydentate ligands for lanthanide nitrates.

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Isolation and Purification of Actinides Using N,O-Hybrid Donor Ligands for Closing the Nuclear Fuel Cycle

Cited by 21 publications

References 178 publications

Selective Complexation and Separation of Uranium(VI) from Thorium(IV) with New Tetradentate N,O-Hybrid Diamide Ligands: Synthesis, Extraction, Spectroscopy, and Crystallographic Studies

Selective Complexation and Separation of Uranium(VI) from Thorium(IV) with New Tetradentate N,O-Hybrid Diamide Ligands: Synthesis, Extraction, Spectroscopy, and Crystallographic Studies

Selective Extraction of Uranium(VI) from Thorium(IV) Using New Unsymmetrical Acidic Phenanthroline Carboxamide Ligands

4-Oxo-7-fluoro-1,10-phenanthroline-2,9-diamides: Synthesis, Structural Features, Lanthanide Complexes, and Am(III)/Ln(III) Solvent Extraction

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