Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

Lewis, Frank W.; Hudson, Michael J.; Harwood, Laurence M.

doi:10.1055/s-0030-1289557

Cited by 66 publications

(24 citation statements)

References 74 publications

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“…A wide range of molecules have been proposed and tested as extractants for solvent extraction in the separation for transmutation processes [6]. The annulated ligand CyMe 4 -BTBP (1 in Fig.…”

Section: Introductionmentioning

confidence: 99%

Characterization of solvents containing CyMe₄-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

et al. 2015

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Radiation stability of CyMe4-BTPhen was examined in systems with three selected cyclohexanone-based diluents. Accelerated electrons were used as a source of ionizing radiation. The CyMe4-BTPhen radiation degradation identification and characterization of the degradation products were performed by high performance liquid chromatography (HPLC) and mass spectrometry (MS) analyses. Residual concentrations of tested ligand were determined. Moreover, extraction properties of the solvents irradiated at two different doses were compared with the extraction properties of non-irradiated solvents to estimate the influence of the presence of degradation products in the organic phase.

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Section: Introductionmentioning

confidence: 99%

Characterization of solvents containing CyMe₄-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

et al. 2015

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“…This separation is necessary, as the lanthanide (Ln) fission products have large neutron absorption cross sections and thereby compromise transmutation efficiency in the nuclear fission process. Selective liquid-liquid extraction of An 3+ from Ln 3+ has been demonstrated using soft nitrogen or sulfur-donor ligands (Madic et al, 2007;Ekberg et al, 2008;Kolarik, 2008;Lewis et al, 2010;Harwood et al, 2011;Hudson et al, 2013;, especially heterocyclic N-donor ligands, e.g. bistriazinylpyridines (BTP) (Case, 1971;Kolarik et al, 1999a,b) and bistriazinylbipyridines (BTBP) (Geist et al, 2006) with separation factors (SFs) for Am 3+ over Eu 3+ greater than 100 (SF = distribution ratio D Am /D Eu ; D M = [M] org /[M] aq ).…”

Section: Introductionmentioning

confidence: 99%

Opportunities and challenges of applying advanced X-ray spectroscopy to actinide and lanthanide N-donor ligand systems

Pruessmann

Nagel

Simonelli

et al. 2022

J Synchrotron Radiat

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N-donor ligands such as n-Pr-BTP [2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine] preferentially bind trivalent actinides (An3+) over trivalent lanthanides (Ln3+) in liquid–liquid separation. However, the chemical and physical processes responsible for this selectivity are not yet well understood. Here, an explorative comparative X-ray spectroscopy and computational (L 3-edge) study for the An/Ln L 3-edge and the N K-edge of [An/Ln(n-Pr-BTP)3](NO3)3, [Ln(n-Pr-BTP)3](CF3SO3)3 and [Ln(n-Pr-BTP)3](ClO4)3 complexes is presented. High-resolution X-ray absorption near-edge structure (HR-XANES) L 3-edge data reveal additional features in the pre- and post-edge range of the spectra that are investigated using the quantum chemical codes FEFF and FDMNES. X-ray Raman spectroscopy studies demonstrate the applicability of this novel technique for investigations of liquid samples of partitioning systems at the N K-edge.

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“…Advanced actinide separation strategies reduce hazards and costs of managing radioactive wastes. As trivalent actinide (An) and lanthanide (Ln) metal ions have similar radii and chemical behavior, small bonding differences in An versus Ln coordination complexes are used to design separation ligands such as heterocyclic N donors. − First synthesized in 1971, 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridines (BTPs) selectively extract Am 3+ , as [Am(BTP) 3 ] 3+ , from Eu 3+ . , Experiment and theory have illuminated the basis for actinide selectivity by BTPs. X-ray diffraction revealed trivalent uranium and lanthanide complexes [M(BTP) 3 ] 3+ in the solid state, − with Ln–N bond lengths consistent with the lanthanide contraction but shortened U–N distances .…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations

Jian

Dan

et al. 2020

J. Phys. Chem. A

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Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here, electrospray ionization was used to generate gas-phase complexes [ML3] 3+ , where M=La, Lu, or Am, and L is the BTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine). Collision induced dissociation (CID) of [ML3] 3+ in the presence of H2O yielded protonated ligand [L(H)] + , and hydroxide [ML2(OH)] 2+ or hydrate [ML(L-H)(H2O)] 2+ where (L-H)is a deprotonated ligand. Whereas solution affinities indicate stronger binding of BTPs towards Am 3+ versus Ln 3+ , the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accord with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3] 3+ versus [LaL3] 3+ , and for both product isomers, [ML2(OH)] 2+ and [ML(L-H)(H2O)] 2+. More facile removal of a ligand from [AmL3] 3+ by CID does not necessarily contradict stronger Am 3+-L binding as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal-ligand bonding.

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Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

Cited by 66 publications

References 74 publications

Characterization of solvents containing CyMe₄-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

Characterization of solvents containing CyMe₄-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

Opportunities and challenges of applying advanced X-ray spectroscopy to actinide and lanthanide N-donor ligand systems

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations

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Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

Cited by 66 publications

References 74 publications

Characterization of solvents containing CyMe4-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

Characterization of solvents containing CyMe4-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

Opportunities and challenges of applying advanced X-ray spectroscopy to actinide and lanthanide N-donor ligand systems

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations

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Characterization of solvents containing CyMe₄-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

Characterization of solvents containing CyMe₄-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons