Separation Of Actinides Research Articles

Membrane Adsorbers with Copolymer Coatings for the Separation of Actinides from Lanthanides (UO22+ and La3+)

Membrane Adsorbers with Copolymer Coatings for the Separation of Actinides from Lanthanides (UO₂²⁺ and La³⁺)

Advancing Rare-Earth (4f) and Actinide (5f) Separation through Machine Learning and Automated High-Throughput Experiments

Advancing Rare-Earth (4<i>f</i>) and Actinide (5<i>f</i>) Separation through Machine Learning and Automated High-Throughput Experiments

Experimental and Kinetic Simulations of Technetium-Catalyzed Hydrazine Oxidation in Nitric Acid Solution

The catalytic reaction of Tc plays a significant role in the chemical separation process during spent fuel reprocessing. However, few studies have been conducted on the chemical reaction mechanism between Tc and hydrazine. Moreover, the instability of Tc(V) and Tc(VI) makes their measurement difficult, rendering many aspects of the reaction process and mechanism unclear. This study investigates the catalytic reaction between Tc and hydrazine in a nitric acid solution. To this end, we obtained the kinetic laws of the reaction under various conditions of acidity, hydrazine concentration, and Tc concentration by monitoring the concentrations of hydrazine and Tc(VII) over time. The reaction kinetics model demonstrated that numerical simulations could effectively predict the reaction process. Results indicated that hydrazine promotes the reduction of Tc(VII) to Tc(IV), constituting the basis for establishing the Tc(IV, V, VI, VII) catalytic cycle. Among these, Tc(V) and Tc(VI) were important active intermediates and the main consumers of hydrazine. The research results may be useful for actinide separation processes based on valence control.

Group hexavalent actinide separation from lanthanides using sodium bismuthate chromatography

Advanced used nuclear fuel (UNF) reprocessing strategies are limited by the complex radiochemical separations and engineering required to achieve the separation of actinides (An) from neutron scavenging lanthanides (Ln). The accessibility of the hexavalent oxidation state for the actinides (U – Am) provides a pathway to achieving a group hexavalent actinide separation from the trivalent lanthanides and Cm. The solid oxidant and ion exchanger, sodium bismuthate (NaBiO3), has been demonstrated to quantitatively oxidize and separate Am from trivalent Cm in a column chromatographic system. This work expands on the use of NaBiO3 chromatography to characterize the adsorption, kinetic, and elution behavior of U, Pu, and Eu. Separation factors over 200 with rapid kinetics were observed at dilute nitric acid concentrations with a complete An/Ln separation achieved in under an hour. The adsorption and chromatographic behavior of key fission products present in various reprocessing raffinates was characterized which demonstrated potential application of a NaBiO3-based separation following a TRUEX process.

Computation-Aided Development of Next-Generation Extractants for Trivalent Actinide and Lanthanide Separation

Computation-Aided Development of Next-Generation Extractants for Trivalent Actinide and Lanthanide Separation

Extraction behaviors of minor actinides and rare earth elements with NTA amide extractants

ABSTRACT Nitrilotriacetamide (NTA amide) has been developed as an extractant for the mutual separation of minor actinides (MA; Am and Cm) and rare earth elements (REs) by solvent extraction. NTA amide is a tertiary amine in which the three carboxyl groups of nitrilotriacetic acid are amidated. NTA amides have six hydrophobic long-chain alkyl groups on the side chains, and they have enhanced solubility in organic solvents, thereby allowing for the use of nonpolar diluents, such as n-dodecane. This study examined the extraction behavior of MA and REs using four NTA amides with six side chains comprising n-octyl groups, 2-ethylhexyl groups, and a mixture of these groups. The results showed that the linear-type hexaoctyl NTA amide (HONTA) had the highest extraction ability for MA. Furthermore, the extraction behavior of MA and REs was different under low and high nitrate conditions, and that of scandium (Sc) was found to be considerably different depending on the side chains.

Coordination Behaviors between Aryl Diamide Amine Ligands and Trivalent Lanthanides: A Spectroscopic and Structural Study

Investigating the complexation of organic ligands with trivalent lanthanides (Ln(III)) is crucial in various fields, particularly in the separation of actinides from lanthanides for spent fuel reprocessing. While alkyl diamide amine ligands have been extensively studied, aryl‐functionalized ligands are rarely reported. To understand the effect of substituents on the coordination mode of diamide amine ligands with Ln(III), two aryl‐substituted diamide amine ligands, 2,2'‐(p‐tolylazanediyl)bis(N‐ethyl‐N‐(p‐tolyl)acetamide) (L1) and 2,2'‐((2‐ethylhexyl)azanediyl)bis(N‐ethyl‐N‐(p‐tolyl)acetamide) (L2), were synthesized and systematically studied. 1H NMR titration showed that metal ion coordination affected the electron density of methylene groups near coordinating atoms more than that of aromatic rings, while fluorescence titration and single‐crystal analysis confirmed 1:1 ligand‐Ln(III) complexes. Compared to alkyl diamide amine ligands, aryl groups increased steric hindrance, enhancing torsional strain and preventing amine nitrogen from participating in complexation, leading to weaker coordination as only two carbonyl oxygen atoms coordinated with Ln(III) in a bidentate mode. This work provides insight into how substituents influence the complexation properties of diamide amine ligands with f‐elements, aiding in the design of new ligands with improved performance.

Amino Acid Decorated Phenanthroline Diimide as Sustainable Hydrophilic Am(III) Masking Agent with High Acid Resistance.

Hydrophilic actinide masking agents are believed to be efficient alternatives to circumvent the extensive hazardous organic solvents/diluents typically employed in the liquid-liquid extraction for nuclear waste management. However, the practical application of hydrophilic ligands faces significant challenges in both synthetic/purification procedures and, more importantly, the acid resistance of the ligands themselves. Herein, we have demonstrated the combination of phenanthroline diimide framework with a biomotif of histidine flanking parts could achieve efficient separation of trivalent lanthanides/actinides (also actinides/actinides) under high acidity of over 1 M HNO3. This approach leverages the soft-hard coordination properties of N, O-hybrid ligands, as well as the energetically favored imides for metal coordination and the multiple protonation of histidine. These factors collectively contribute to the synthesis of an easily accessible, highly water-soluble, superior selective, and acid-resistant Am(III) masking agent. Thus, we have shown in this paper, by proper combination of synthetic N, O-hybrid ligand with amino acid, trivalent lanthanide and actinide separation could be efficiently fulfilled in a more sustainable manner.

A Theoretical Study on the Influence of Five- and Six-Membered N-Heterocyclic Ring Side Chains of the N-Donor Extractants on Am(III)/Eu(III) Extraction and Separation.

According to the green development requirements of carbon neutrality and carbon peaking, the effective separation of lanthanides and actinides is one of the key factors for nuclear energy to become a sustainable energy source. In recent years, o-phenanthroline-based ligands have been proven to be effective in the separation of lanthanides and actinides. In this work, based on 5,9b-dihydro-4aH-cyclopenta[1,2-b:5,4-b']dipyridines, we designed six N-heterocyclic ring ligands and theoretically studied their extraction capacity and separation selectivity for the Am(III) and Eu(III) ions. Various theoretical methods were used to analyze the properties of the ligands and study the bonding nature of the ligands with the metal ions. Thermodynamic parameters were calculated to measure the extraction ability of the ligands to the metal ions and to explore the separation capacity of the ligand for the Am(III) and Eu(III) ions. The calculated results show that the five- and six-membered N-heterocyclic ring side chains of the ligands and the distribution of the N atoms on the side chain rings have obvious effects on the bonding of the ligands to metal ions and on the extraction and separation properties of the ligands for the metal ions. It was found that the extractants with six-membered ring side chains possess an extraction ability slightly better than that of the ligands with five-membered ring side chains and that the ligands with a pair of adjacent N atoms on the side chains have a stronger separation selectivity for the Am(III)/Eu(III) ions. The theoretical research in this work will help to understand the details of binding and extraction properties of similar ligands and provide insights for the future design of five- and six-membered heterocyclic ligands.

6-(6-Methyl-1,2,4,5-Tetrazine-3-yl)-2,2'-Bipyridine: A N-Donor Ligand for the Separation of Lanthanides(III) and Actinides(III).

Here, we report the synthesis of the 6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2'-bipyridine (MTB) ligand that has been developed for lanthanide/actinide separation. A multimethod study of the complexation of MTB with trivalent actinide and lanthanide ions is presented. Single-crystal X-ray diffraction measurements reveal the formation of [Ce(MTB)2(NO3)3], [Pr(MTB)(NO3)3H2O], and [Ln(MTB)(NO3)3MeCN] (Ln = Nd, Sm, Eu, Gd). In addition, the complexation of Cm(III) with MTB in solution was studied by time-resolved laser fluorescence spectroscopy. The results show the formation of [Cm(MTB)1-3]3+ complexes, which occur in two different isomers. Quantum chemical calculations reveal an energy difference between these isomers of 12 kJ mol-1, clarifying the initial observations made by time-resolved laser fluorescence spectroscopy (TRLFS). Furthermore, quantum theory of atoms in molecules (QTAIM) analysis of the Cm(III) and Ln(III) complexes was performed, indicating a stronger covalent contribution in the Cm-N interaction compared to the respective Ln-N interaction. These findings align well with extraction data showing a preferred extraction of Am and Cm over lanthanides (e.g., max. SFAm/Eu = 8.3) at nitric acid concentrations <0.1 mol L-1 HNO3.

Diglycolamic Acid-Functionalized MWCNT-Augmented Polymeric Beads for Efficient Separation of Trivalent Lanthanides and Actinides

Diglycolamic Acid-Functionalized MWCNT-Augmented Polymeric Beads for Efficient Separation of Trivalent Lanthanides and Actinides

Exploring the bonding and extraction separation effects of N donor ligands with different skeletons on Am(III) and Eu(III)

Designing ligands for effective separation of actinide(III)/lanthanide(III) is one of the key issues in the treatment of spent nuclear fuel. However, due to the chemical similarity of trivalent actinides and lanthanides, their separation faces a great challenge in the reprocessing of spent nuclear fuel. Nitrogen donor extractants are considered as promising reagents for separation of trivalent actinides and lanthanides. To the best of our knowledge, the pre-organized structure of the ligand has a strong influence on the extraction separation capacity. In this work, we designed four N-donor ligands (L1 and L2 with pyridine and bipyridine skeletons, respectively, and L3 and L4 both with phenanthroline skeletons) with different pre-organized structures and investigated their selective extraction for Am(III) and Eu(III) by using scalar relativistic density functional theory (DFT). The absolute minimum ESP values of these ligands and the higher HOMO level suggest that the ligand L2 may have a stronger affinity for Am(III)/Eu(III) ions than other ligands. The three average bond lengths of each complex indicate that the Am(III) and Eu(III) ions have larger bond lengths with N2 atoms than with N1 atoms. Various theoretical approaches have been used to evaluate the properties of the four ligands as well as the coordination structures, bonding properties and thermodynamic properties of the complexes of the four ligands with Am(III) and Eu(III). The WBIs, QTAIM, NBO, DOS and EDA analysis indicate that the metal–ligand bonds are mainly ionic in character, the Am-N bond has more covalency than the Eu-N bond because the Am 5f orbitals are more involved in bonding with ligand than Eu 4f orbitals. According to the extended transition state and natural orbital chemical valence theory (ETS-NOCV) analysis, electrons are obviously transferred from the lone pair of the ligand N atom to the hybrid s, d and f orbitals of the metal ion. The thermodynamic results show that the four ligands can coordinate well with the Am and Eu ions, and also have suitable separation capacity for Am and Eu. Among the four ligands, the L2 and L3 ligands have the strongest coordination ability for metals and the best extraction separation effect for Am and Eu. It can be seen that the bridging skeleton of the ligand and the number of N atoms on the five-membered ring and also different organic solvents have obvious effects on the extraction and separation capacity of the ligand. This study provides a theoretical basis for the efficient separation of Am(III)/Eu(III) by adjusting the preorganization level of ligands, and provides a theoretical basis for the design and screening of ligands by preorganization.

Synthesis of Fused [1,2,3]-Triazoloheteroarenes via Intramolecular Azo Annulation of N-Tosylhydrazones Catalyzed by 1,8-Diaza-bicyclo[5.4.0]undec-7-ene.

The structural diversity of triazoloheteroarenes render this moiety an attractive synthon for drug discovery, C-H functionalization, and complexant design for minor actinide separations. While contemporary work has demonstrated the capacity to leverage downstream functional group interconversion of the triazolopyridine, a broadly applicable method tolerant of diverse heteroaryl constructs and pendant functionality to obtain triazoloheteroarenes remains under reported. In this work, the serendipitous discovery of a metal, azide, and oxidant free transformation of various heteroaryl N-tosylhydrazones of carbaldehydes and ketones to the corresponding [1,2,3]-triazoloheteroarene via intramolecular azo annulation using a substoichiometric amount of 1,8-diaza-bicyclo[5.4.0]undec-7-ene is described. These results substantively improve upon previous approaches offering efficient access to the described heterocycles. Discovery of reaction conditions, method optimization, complexant, pyridine, and heteroarene substrate scope, as well as relevant scale-up reactions are reported herein.

Next-Generation 3,3'-AlkoxyBTPs as Complexants for Minor Actinide Separation from Lanthanides: A Comprehensive Separations, Spectroscopic, and DFT Study.

Progress toward the closure of the nuclear fuel cycle can be achieved if satisfactory separation strategies for the chemoselective speciation of the trivalent actinides from the lanthanides are realized in a nonproliferative manner. Since Kolarik's initial report on the utility of bis-1,2,4-triazinyl-2,6-pyridines (BTPs) in 1999, a perfect complexant-based, liquid-liquid separation system has yet to be realized. In this report, a comprehensive performance assessment for the separation of 241Am3+ from 154Eu3+ as a model system for spent nuclear fuel using hydrocarbon-actuated alkoxy-BTP complexants is described. These newly discovered complexants realize gains that contemporary aryl-substituted BTPs have yet to achieve, specifically: long-term stability in highly concentrated nitric acid solutions relevant to the low pH of unprocessed spent nuclear fuel, high DAm over DEu in the economical, nonpolar diluent Exxal-8, and the demonstrated capacity to complete the separation cycle with high efficiency by depositing the chelated An3+ to the aqueous layer via decomplexation of the metal-ligand complex. These soft-N-donor BTPs are hypothesized to function as bipolar complexants, effectively traversing the organic/aqueous interface for effective chelation and bound metal/ligand complex solubility. Complexant design, separation assays, spectroscopic analysis, single-crystal X-ray crystallographic data, and DFT calculations are reported.

Determination of 93Zr, 237Np and Th radionuclides in radioactive waste and mineral samples: extension of the method for determination of actinides

A novel method has been developed for the simultaneous determination of difficult-to-measure (DTM) nuclides 93Zr, 237Np, 232Th, 230Th and 228Th using a DGA resin® (containing N,N,N′,N′-tetra-n-octyl-diglycolamide) column for simultaneous separation of Zr and actinides followed by purification of Zr, Np and Th on a TEVA resin® (containing Aliquat 336) column. Samples are destroyed by fusion with sodium hydroxide or by acid destruction using HNO3, HCl and HF. Pre-concentration procedure tailored to the extraction chromatography is based on co-precipitation of Zr and actinides and removal of alumina, silica, iron and calcium. The concentrations of 93Zr, 237Np and Th nuclides are determined by ICP-MS and α spectrometry, respectively. High chemical recoveries (≥ 73%) and separation factors were obtained for Zr, Np and Th both in evaporation concentrates of an NPP and various samples of mineral origin such as soil and concrete. The procedure can be easily combined with the simultaneous separation of other actinides (Pu, Am, U) using the same DGA column that has been described in our previous papers (Cassette et al. in Appl Radiat Isot 68:122–130, 2010 and Groska et al. in J Radioanal Nucl Chem 309(3):1145–1158, 2016).

Shape-Selective Supramolecular Capsules for Actinide Precipitation and Separation.

Improving actinide separations is key to reducing barriers to medical and industrial actinide isotope production and to addressing the challenges associated with the reprocessing of spent nuclear fuel. Here, we report the first example of a supramolecular anion recognition process that can achieve this goal. We have designed a preorganized triamidoarene receptor that induces quantitative precipitation of the early actinides Th(IV), Np(IV), and Pu(IV) from industrially relevant conditions through the formation of self-assembled hydrogen-bonded capsules. Selectivity over the later An(III) elements is shown through modulation of the nitric acid concentration, and no precipitation of actinyl or transition-metal ions occurs. The Np, Pu, and Am precipitates were characterized structurally by single-crystal X-ray diffraction and reveal shape specificity of the internal hydrogen-bonding array for the encapsulated hexanitratometalates. This work complements ion-exchange resins for 5f-element separations and illustrates the significant potential of supramolecular separation methods that target anionic actinide species.

Enhancing the Selectivity of Trivalent Actinide over Lanthanide Using Asymmetrical Phenanthroline Diamide Ligands.

Phenanthroline diamide ligands have been widely used in the separation of trivalent actinides and lanthanides, but little research has focused on extractants with asymmetrical substitutes. Two novel asymmetrical phenanthroline-based ligands N2,N2,N9-triethyl-N9-tolyl-1,10-phenanthroline-2,9-dicarboxamide (DE-ET-DAPhen) and N2-ethyl-N9,N9-dioctyl-N2-tolyl-1,10-phenanthroline-2,9-dicarboxamide (DO-ET-DAPhen) were first synthesized in this work, whose extraction ability and complexation mechanism to trivalent actinides [An(III)] and lanthanides [Ln(III)] were systematically investigated. The ligands dissolved in n-octanol exhibit good extraction ability and high selectivity toward Am(III) in acidic solutions. The complexation mechanism of the ligands with Ln(III) in solution and solid state was analyzed using slope analysis, 1H NMR spectrometric titration, ESI-MS, and calorimetric titration. It is revealed that the ligands complex with Am(III)/Eu(III) with 1:1 stoichiometry. The stability constant (log β) of the complexation reaction of Eu(III) with DE-ET-DAPhen determined by UV-vis spectrophotometric and calorimetric titration is higher than that of DO-ET-DAPhen, indicating the stronger complexation ability of DE-ET-DAPhen. Meanwhile, the calorimetric titration results show that the complexation process is exothermic with a decreased entropy. The structures of 1:1 complexes of Eu(III) and Nd(III) with DE-ET-DAPhen were analyzed through single-crystal X-ray diffraction. This work proves that ligands containing asymmetrical functional groups are promising for An(III)/Ln(III) separation, which shows great significance in efficient extractants designed for the spent nuclear fuel reprocessing process.

Complexation and extraction of trivalent actinides over lanthanides using highly soluble phenanthroline diamide ligands with different side chains

Although phenanthroline diamide ligands have been widely reported, their limited solubility in organic solvents and poor performance in the separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) at high acidity are still clear demerits. In this study, we designed and synthesized three highly soluble phenanthroline diamide ligands with different side chains. By introducing alkyl chains and ester groups, the ligands solubility in 3-nitrotrifluorotoluene is increased to over 600 mmol/L, significantly higher than the previous reported phenanthroline diamide ligands. Based on anomalous aryl strengthening, benzene ring was incorporated to enhance ligand selectivity toward Am(III). Extraction experiments demonstrated favorable selectivity of all the three ligands towards Am(III). The optimal separation factor (SFAm/Eu) reaches 53 at 4 mol/L HNO3, representing one of the most effective separation of An(III) over Ln(III) under high acidity. Slope analysis, single crystal structure analysis, as well as titration of ultraviolet visible spectroscopy, mass spectrometry, and nuclear magnetic resonanc confirmed the formation of 1:1 and 1:2 complex species between the metal ions and the ligands depending on the molar ratio of metal ions in the reaction mixture. The findings of this study offer valuable insights for developing phenanthroline diamide ligands for An(III)/Ln(III) separation.

Theoretical investigation on the ligands constructed from phenanthroline and five-membered N-heterocyclic rings for bonding and separation properties of Am(III) and Eu(III).

The ligands, derived from the combination of phenanthroline and various five-membered N-heterocyclic rings, were subject to a comprehensive investigation for their potential in the extraction and separation of actinides and lanthanides. This study employed DFT methods to thoroughly explore the properties of both phenanthroline (Ph) and the diverse five-membered N-heterocyclic rings (R1-R8). Additionally, tridentate ligands RlPh (l = 1-8) and tetradentate ligands RlPhRr (l, r = 1-8) were analyzed in detail, encompassing their electrostatic potential (ESP), protonation energy, coordination bonding with the metals Am(III) and Eu(III), and the thermodynamics of extraction separation for Am(III) and Eu(III). The findings highlight that the electrostatic potential (ESP) and binding capabilities of the five-membered N-heterocyclic ring units serve as effective predictors for the properties of intricate tridentate and tetradentate ligands, as well as their coordination bonding affinity with metals. The ligands' binding energy is closely associated with their ESP, and notably, the binding energy of tridentate and tetradentate ligands correlates well with the binding energies of their constituent structural units. The computational results reveal that the R2 unit, along with its corresponding tridentate ligand R2Ph and tetradentate ligands R2PhRr, exhibits the highest ESP, superior binding energies, and the strongest coordination bonding affinity with the metals. The theoretical calculations further identify several promising extractants for the effective separation of Am(III) and Eu(III). The tridentate ligands R1Ph, R7Ph, and R4Ph, and the tetradentate ligands R4PhR4, R6PhR6, R2PhR2, R1PhR5 and R3PhR6 were identified as having excellent separation performance for Am(III) and Eu(III). This study would provide insights for the design of extractants for the separation of Am(III) and Eu(III) by use of five-membered N-heterocyclic rings as structural units.

Interlayer confinement mediated oxidation of americium by sodium bismuthate and stability of its higher redox states in acidic solution.

Mutual separation of trans-plutonium actinides (Ans) from lanthanides (Lns) or adjacent Ans is challenging as they exhibit great chemical similarity. Selective Am oxidation-based Am-Lns or Am-Cm separation strategies give very high separation factors. There exist several reports on different aspects of Am3+ oxidation by NaBiO3·xH2O (x = 2-3), which suggests that the oxidation mechanism is still not well understood. We, therefore, carefully performed several experiments taking advantage of the difference in the redox chemistry of Eu3+ and Am3+. The ion exchange of Eu3+ with the interlayer Na+ in NaBiO3 was confirmed by an ionic strength variation experiment. The shift in the 001 peak of NaBiO3 in XRD and the appearance of peaks corresponding to the trivalent Ln ions in XRF after Ln3+ loading give direct evidence for Na+ exchange with Ln3+. The stability of the higher oxidation state of Am was monitored spectrophotometrically. The experimental investigations also suggested the role of Am3+ → AmO22+ transformation in NaBiO3·xH2O (x = 2-3) dissolution even at pH ∼ 1, which otherwise is difficult to achieve even with >1 M HNO3. The role of colloidal NaBiO3 particles and dissolved BiO3- in controlling or stabilizing different oxidation states of Am was also discussed.