New route to amide-functionalized N-donor ligands enables improved selective solvent extraction of trivalent actinides

Bulmer, Rachel; Spencer, Thomas B.; Wilden, Andreas; Modolo, Giuseppe; Vu, Trong-Hung; Simonin, Jean‐Pierre; Lewis, Frank W.

doi:10.1039/d2cc03876e

“…This is an improvement over previous BTP complexants that limit either complexant or HNO 3(aq) concentration due to formation of aggregates, precipitates, or emulsion during phase contact. 18 The distribution ratios of both 241 Am 3+ and 154 Eu 3+ increased with increasing complexant concentration under a constant initial acid concentration of 5 M (Fig. 2).…”

mentioning

confidence: 90%

“…This is an improvement over previous BTP complexants that limit either complexant or HNO 3(aq) concentration due to formation of aggregates, precipitates, or emulsion during phase contact. 18…”

mentioning

confidence: 99%

A hydrolytically stable complexant for minor An separation from Ln in process relevant diluents

Fletcher,

Tedder,

Olayiwola

et al. 2024

Chem. Commun.

0

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“…Due to the high experimental cost caused by the high radioactivity of actinides, a computational chemistry approach has been found to be necessary to study lanthanide and actinide separation . Thus, we conducted a thorough analysis of the extraction of bipyridine phosphate ligands through relativistic quantum chemical computations, examining their impact on the Am(III)/Eu(III) separation across various nitric acid solutions.…”

Section: Introductionmentioning

confidence: 99%

“…Due to the high experimental cost caused by the high radioactivity of actinides, a computational chemistry approach has been found to be necessary to study lanthanide and actinide separation. 21 Thus, we conducted a thorough analysis of the extraction of bipyridine phosphate ligands through relativistic quantum chemical computations, examining their impact on the Am(III)/Eu(III) separation across various nitric acid solutions. The study particularly delved into several issues, including molecular structure, electrostatic potential (ESP), and the MOs model of bipyridyl phosphate ligands: structure, bonding properties, molecular MOs, and thermodynamic behavior of complexes formed by Am(III) and Eu(III) with bipyridyl phosphate ligands.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Am(III) and Eu(III) Separation by a Bipyridyl Phosphate Ligand

Zhang,

Ye,

Chen

et al. 2024

ACS Omega

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Actinide An(III) and lanthanide Ln(III) are known to exhibit similar chemical properties; thus, it is difficult to distinguish them in the separation of highly radioactive waste liquids. One potential method to efficiently separate actinides and lanthanides involves the design and development of phosphorus−oxygen-bonded ligands with solvent extraction separation. Here, a bipyridine phosphate ligand with two isopropyl and phosphate groups is introduced to selectively extract actinides. The electronic structure, bonding properties, thermodynamic behavior, and quantum theory of atoms in molecules (QTAIM) of Am(III) and Eu(III) complexes with the bipyridine phosphate ligands were analyzed by using density functional theory (DFT) calculations. The analysis demonstrates that the Am−N bond exhibits stronger covalent characteristics than the Eu−N bond, indicating that the bipyridine phosphate ligand had better selectivity for Am(III) than for Eu(III) in terms of binding affinity. The thermodynamic analysis established the complex [ML(NO 3 ) 2 (H 2 O) 2 ] + as the most stable species during the complexation process. The results indicate great potential for utilizing the bipyridine phosphate ligand for the effective separation of An(III)/Ln(III) in spent fuel reprocessing experiments.

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“…This high-level liquid waste (HLLW) is then subjected to the partitioning and transmutation (P&T) process to separate the radioactive minor Ans chemically and transmute them into short-lived nuclides though neutron bombarding. The prerequisite for P&T lies in the efficient separation of Lns from Ans due to the large neutron cross section of Lns. ,− …”

Section: Introductionmentioning

confidence: 99%

A Simple yet Efficient Hydrophilic Phenanthroline-Based Ligand for Selective Am(III) Separation under High Acidity

Tian

¹

,

Liu

²

,

Kang

³

et al. 2023

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Highly selective hydrophilic ligands were believed to be an efficient way to overcome the massive amount of hazardous organic solvent used in the liquid−liquid extraction process and stood as a new frontier in the Lns(III)/Ans(III) partition. Current reported hydrophilic ligands suffer from harsh preparation conditions, inferior extraction performances, limited available chemical structures, and inability to carry out extraction under high acidity. In this article, we report a simple yet efficient carboxylic group modified phenanthroline-diimide ligand which displayed unexpected Lns(III)/Ans(III) and Ans(III)/Ans(III) separation capabilities in 1.5 M HNO 3 . Unique dimeric architectures for Eu(III) complexes were observed, which could be the origin of the outperforming selectivity and acid resistance. We believe this crystal engineering approach could inspire a renaissance in searching for new functional groups and coordination modes for efficient, highacid-tolerance Lns(III)/Ans(III) separation ligands.

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New route to amide-functionalized N-donor ligands enables improved selective solvent extraction of trivalent actinides

Abstract: A new general synthetic route to selective actinide extracting ligands for spent nuclear fuel reprocessing has been established. The amide-functionalized ligands separate Am(III) and Cm(III) from the lanthanides with high...

Cited by 3 publications

References 31 publications

A hydrolytically stable complexant for minor An separation from Ln in process relevant diluents

A hydrolytically stable complexant for minor An separation from Ln in process relevant diluents

Theoretical Study of Am(III) and Eu(III) Separation by a Bipyridyl Phosphate Ligand

A Simple yet Efficient Hydrophilic Phenanthroline-Based Ligand for Selective Am(III) Separation under High Acidity

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