Tuning the Alkyl Chain of Nitrilotriacetamide for Selectively Extracting Trivalent Am over Eu Ions.

The successful management and safe disposal of high-level nuclear waste necessitate the efficient separation of actinides (An) from lanthanides (Ln), which has emerged as a crucial prerequisite. Mixed donor ligands incorporating both soft and hard donor atoms have garnered interest in the field of An/Ln separation and purification. One such example is nitrilotriacetamide (NTAamide) derivatives, which have demonstrated selectivity in extracting minor actinide Am(III) ions over Eu(III) ions. Nevertheless, the Am/Eu complexation behavior and selectivity remain underexplored. In the work, a comprehensive and systematic investigation has been conducted for [M(RL)(NO3)3] complexes (M = Am and Eu) utilizing relativistic density functional theory. The NTAamide ligand (RL) is substituted with various alkyl groups, namely, methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Thermodynamic calculations show that the alkyl chain length in NTAamide is capable of tuning the separation selectivity of Am and Eu. Moreover, the differences in calculated free energies between Am and Eu complexes are more negative for R = Bu-Oct than Me-Pr. This indicates that elongation of the alkyl chain can increase the efficiency of selective separation of Am(III) from Eu(III). Based on the quantum theory of atoms in molecules and charge decomposition analyses, it has been observed that the strength of Am-RL bonds is higher than that of Eu-RL bonds. This disparity is attributed to a greater degree of covalency in Am-RL bonds and a higher level of charge transfer from ligands to Am within complexes containing these bonds. Energies of occupied orbitals with the central N character are recognized overall lower for [Am(OctL)(NO3)3] than for [Eu(OctL)(NO3)3], indicative of stronger complexation stability of the former. These results offer valuable insights into the separation mechanism of NTAamide ligands, which can help guide the development of more powerful agents for An/Ln separation in future applications.

Complexation of a Nitrilotriacetate-Derived Triamide Ligand with Trivalent Lanthanides: A Thermodynamic and Crystallographic Study.

Non-heterocyclic N-donor nitrilotriacetate-derived triamide ligands are one of the most promising extractants for the selective extraction separation of trivalent actinides over lanthanides, but the thermodynamics and mechanism of the complexation of this kind of ligand with actinides and lanthanides are still not clear. In this work, the complexation behaviors of N,N,N',N',N″,N″-hexaethylnitrilotriacetamide (NTAamide(Et)) with four representative trivalent lanthanides (La3+, Nd3+, Eu3+, and Lu3+) were systematically investigated by using 1H nuclear magnetic resonance (1H NMR), ultraviolet-visible (UV-vis) and fluorescence spectrophotometry, microcalorimetry, and single-crystal X-ray diffractometry. 1H NMR spectroscopic titration of La3+ and Lu3+ indicates that two species of 1:2 and 1:1 metal-ligand complexes were formed in NO3- and ClO4- media. The stability constants of NTAamide(Et) with Nd3+ and Eu3+ obtained by UV-vis and fluorescence titration show that the complexing strength of NTAamide(Et) with Nd3+ is lower than that with Eu3+ in the same anionic medium, while that of the same lanthanide complex is higher in ClO4- medium than in NO3- medium. Meanwhile, the formation reactions for all metal-ligand complexes are driven by both enthalpy and entropy. The structures of lanthanide complexes in the single ClO4- and NO3- medium and the mixed one were determined to be [LnL2(MeOH)](ClO4)3 (Ln = La, Nd, Eu, and Lu), [LaL2(EtOH)2][La(NO3)6], and [LaL2(NO3)](ClO4)2, separately. The average bond lengths of lanthanide complexes decrease gradually with the decrease in ionic radii of Ln3+, indicating that heavier lanthanides form stronger complexes due to the lanthanide contraction effect, which coincides with the trend of the complexing strength obtained by spectroscopic titration. This work not only reveals the thermodynamics and mechanism of the complexation between NTAamide ligands and lanthanides but also obtains the periodic tendency of complexation between them, which may facilitate the separation of trivalent lanthanides from actinides.

Extraction and Complexation Investigation of Palladium(II) by a Nitrilotriacetate-Derived Triamide Ligand.

Effective and selective separation and recovery of the fission product palladium from high-level liquid waste are conducive not only to reducing its hazards to the public health and environment but also to alleviate the pressure on the increasing demand for natural palladium. Herein, the Pd2+ extraction in an HNO3 solution with a nitrilotriacetate-derived triamide ligand NTAamide(n-Oct) and the complexation between them were investigated. Using n-octanol as a diluent, NTAamide(n-Oct) demonstrated an excellent selectivity, strong extractability, and high loading capacity for Pd2+ extraction. Combined with the results of single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, electrospray ionization-mass spectroscopy, microcalorimetric titration, and slope analysis, the extracted complexes were determined as [PdL2](NO3)2 and [PdL2][Pd(NO3)4] (where L denotes the NTAamide ligand) in 0.10 and 3.0 mol/L HNO3 solutions, respectively. The extraction model closely depended on the solvation state of Pd2+ in the HNO3 solution. An ion-pair extraction model was proposed and discussed.

Theoretical Investigation of Catalytic Water Splitting by the Arene-Anchored Actinide Complexes.

Actinide complexes, which could enable the electrocatalytic H2O reduction, are not well documented because of the fact that actinide-containing catalysts are precluded by extremely stable actinyl species. Herein, by using relativistic density functional theory calculations, the arene-anchored trivalent actinide complexes (Me,MeArO)3ArAn (marked as [AnL]) with desirable electron transport between metal and ligand arene are investigated for H2 production. The metal center is changed from Ac to Pu. Electron-spin density calculations reveal a two-electron oxidative process (involving high-valent intermediates) for complexes [AnL] (An = P-Pu) along the catalytic pathway. The electrons are provided by both the actinide metal and the arene ring of ligand. This is comparable to the previously reported uranium catalyst (Ad,MeArO)3mesU (Ad = adamantine and mes = mesitylene). From the thermodynamic and kinetic perspectives, [PaL] offers appreciably lower reaction energies for the overall catalytic cycle than other actinide complexes. Thus, the protactinium complex tends to be the most reactive for H2O reduction to produce H2 and has the advantage of its experimental accessibility.

A H-Bonding and Electrostatic Interaction Combined Strategy for TcO4- Separation by a Nitrotriacetate-Derived Amine-Amide Extractant.

Effective and selective separation of technetium from acidic nuclear liquid waste is highly desirable for partitioning and transmutation but is of significant challenge. Highly efficient extraction of pertechnetate can be achieved by taking H-bonding and electrostatic interaction combined strategy. Base on this strategy, an amine-amide ligand NTAamide(n-Oct) was employed to extract TcO4- in HNO3 solution. Using n-dodecane as a diluent, NTAamide(n-Oct) demonstrated excellent extractability and good selectivity toward TcO4- with a rapid extraction equilibrium that could be reached in less than 1 min. Its maximal loading capacity for TcO4- was almost 100 times as much as that of traditional amine extractant Aliquat-336 nitrate. Meanwhile, TcO4- could be efficiently stripped from the loaded organic phase by (NH4)2CO3 solution. Slope analysis indicated the formation of a 1:1 complex of NTAamide(n-Oct) with TcO4-. The extraction conformed to the anion exchange extraction model, as confirmed by analyses of single-crystal X-ray diffraction, 1H NMR titration, FTIR, and ESI-MS.

Highly Selective Separation of Actinides from Lanthanides by Dithiophosphinic Acids: An in-Depth Investigation on Extraction, Complexation, and DFT Calculations.

To further reveal the extraction model for selective separation of trivalent actinides over lanthanides by dithiophosphinic acids (DPAHs), five representative DPAH ligands with different substituent groups have been synthesized, and their extraction and complexation behaviors toward Am3+/Eu3+ have been investigated both experimentally and theoretically. The introduction of electron-withdrawing group -CF3 into DPAH ligands is beneficial to their extractability among the five ligands. Slope analyses show that both Am3+ and Eu3+ were extracted as tetra-associated species with DPAH ligands. In addition, the results obtained from luminescence spectroscopy, Raman spectroscopy, and ESI-MS suggest that all of the five DPAHs coordinate with Eu3+ mainly in the form of ML3(HL)(H2O) (L represents deprotonated DPAH). Density functional theory (DFT) calculations on the thermodynamic parameters illustrate that the extractability of DPAHs is dominated by the deprotonation property of these ligands. Meanwhile, molecular orbital analysis indicates that the unoccupied valence orbitals of Am3+ display a stronger affinity to the sulfur lone electron pair than those of Eu3+, which should be one of the key factors contributing to the excellent selectivity of Am3+ over Eu3+ by DPAH ligands.

Highly Efficient Trivalent Americium/Europium Separation by Phenanthroline-Derived Bis(pyrazole) Ligands.

The synthesis, Eu3+ complexation, and solvent extraction of Am3+ and Eu3+ from nitric acid solutions by tetradentate phenanthroline-derived bis(pyrazole) (BPPhen) ligands were described. By using meta-nitrobenzotrifluoride as diluent, BPPhen ligands in combination with 2-bromohexanoic acid extracted Am3+ and Eu3+ with remarkably high efficiency, excellent selectivity, and fast extraction kinetics. Stripping posed no issues. The ligands also showed excellent hydrolytic stability and acid tolerance. 2-Bromohexanoic anion neutralized the charge and increased the lipophilicity of the extracted ion pair. The extraction conformed to a cation exchange model. Slope analysis demonstrated the extraction of 1:2 metal/ligand complexes. Analyses by electrospray ionization mass spectrometry, time-resolved laser-induced fluorescence spectroscopy, Raman, and Fourier transform infrared techniques indicated that the composition of the extracted species is [Eu(nOct-BPPhen)2(H2O)]3+. The formation of 1:2 complexes was also confirmed by UV-vis spectroscopic titration and microcalorimetric titration methods. Meanwhile, the stability constants ( K) and the thermodynamic parameters (Δ H, Δ S, Δ G) for the complexation of Eu3+ with nOct-BPPhen were presented too.

Selective Extraction of Americium(III) over Europium(III) with the Pyridylpyrazole Based Tetradentate Ligands: Experimental and Theoretical Study.

1,3-Bis[3-(2-pyridyl)pyrazol-1-yl]propane (Bippp) and 1,2-bis[3-(2-pyridyl)pyrazyl-1-methyl]benzene (Dbnpp), the pyridylpyrazole based tetradentate ligands, were synthesized and characterized by MS, NMR, and FT-IR. The solvent extraction and complexation behaviors of Am(III) and Eu(III) with the ligands were investigated experimentally and theoretically. In the presence of 2-bromohexanoic acid, the two ligands can effectively extract Am(III) over Eu(III) and other rare earth(III) metals (RE(III)) in HNO3 solution with the separation factors (SFAm/RE) ranging from 15 to 60. Slope analyses showed that both Am(III) and Eu(III) were extracted as monosolvated species, which agrees well with the results observed from X-ray crystallography and MS analyses. The stability constants (log K) obtained from UV-vis titration for Eu(III) complexes with Bippp and Dbnpp are 4.75 ± 0.03 and 4.45 ± 0.04, respectively. Both UV-vis titration and solvent extraction studies indicated that Bippp had stronger affinity for Eu(III) than Dbnpp, which is confirmed by density functional theory (DFT) calculations. DFT calculations revealed that the AmL(NO3)3 (L = Bippp and Dbnpp) complexes are thermodynamically more stable in water than their Eu(III) analogues, which is caused by greater covalency of the Am-N than Eu-N bonds. Theoretical studies gave an insight into the nature of the M(III)-ligand bonding interactions.

Influence of a bridging group and the substitution effect of bis(1,2,4-triazine) N-donor extractants on their interactions with a Np(V) cation.

The present theoretical study provides a realistic evaluation of the equilibrium structure, reaction modes, and bonding characteristics of a variety of neptunyl complexes formed with bis(triazinyl) N-donor extractants, which differ in their bridging groups such as pyridine, bipyridines, and orthophenanthroline, corresponding to the ligands (L) of tridentate bis(triazinyl)pyridines and tetradentate bis(triazinyl)bipyridines and bis(triazinyl)-1,10-phenanthrolines (BTPhens), respectively. Our calculations show that coordination of [NpO2](+) to tetradentate ligands is more favorable than that to tridentate ones no matter in a gas, aqueous, or organic phase. The presence of nitrate ions can enhance the coordination ability of neptunyl and stabilize the neutral NpO2L(NO3) complexes in thermodynamics. Our studies indicate that the complexation reaction mode [NpO2(H2O)n](+) + L + NO3(-) → NpO2L(NO3) + nH2O is the most probable at the interface between water and the organic phase. The contribution of an orthophenanthroline bridging group is relatively more pronounced compared to its pyridine counterpart in ligand-exchange reaction. Complexation reactions of hydrated neptunyl with C2-BTPhen and BTPhen assisted by a nitrate ion are favorable thermodynamically, resulting from the least deformation of the ligand and strong complexation stability. The quantum theory of atoms-in-molecules and charge decomposition analysis suggest that electron delocalization and charge transfer are the main reasons responsible for stabilization of the tetradentate complexes and reveal a strong ionic feature of the Np-ligand bonds. Inspection of the frontier molecular orbitals reveals a distinct 5f orbital (Np) interaction with ligand atoms, implying the extent of f-based covalency. Our study may facilitate the rational design of ligands toward the improvement of their binding ability with Np(V) and more efficient separation of Np in spent nuclear fuels.

From "S" to "O": experimental and theoretical insights into the atmospheric degradation mechanism of dithiophosphinic acids.

Dithiophosphinic acids (DPAHs, expressed as R1R2PSSH) are a type of sulfur-donor ligand that have been vastly applied in hydrometallurgy. In particular, DPAHs have shown great potential in highly efficient trivalent actinide/lanthanide separation, which is one of the most challenging tasks in separation science and is of great importance for the development of an advanced fuel cycle in nuclear industry. However, DPAHs have been found liable to undergo oxidative degradation in the air, leading to significant reduction in the selectivity of actinide/lanthanide separation. In this work, the atmospheric degradation of five representative DPAH ligands was investigated for the first time over a sufficiently long period (180 days). The oxidative degradation process of DPAHs elucidated by ESI-MS, 31P NMR, and FT-IR analyses is R1R2PSSH → R1R2PSOH → R1R2POOH → R1R2POO-OOPR1R2, R1R2PSSH → R1R2PSS-SSPR1R2, and R1R2PSSH → R1R2PSOH → R1R2POS-SOPR1R2. Meanwhile, the determination of pK a values through pH titration and oxidation product by PXRD further confirms the S → O transformation in the process of DPAH deterioration. DFT calculations suggest that the hydroxyl radical plays the dominant role in the oxidation process of DPAHs and the order in which the oxidation products formed is closely related to the reaction energy barrier. Moreover, nickel salts of DPAHs have shown much higher chemical stability than DPAHs, which was also elaborated through molecular orbital (MO) and adaptive natural density portioning (AdNDP) analyses. This work unambiguously reveals the atmospheric degradation mechanism of DPAHs through both experimental and theoretical approaches. At the application level, the results not only provide an effective way to preserve DPAHs but could also guide the design of more stable sulfur-donor ligands in the future.

Interaction between U and Th on their uptake, distribution, and toxicity in V S. alfredii based on the phytoremediation of U and Th.

Variant Sedum alfredii Hance (V S. alfredii) could simultaneously take up U and Th from water with the highest concentrations recorded as 1.84 × 104 and 6.72 × 103 mg/kg in the roots, respectively. Th stimulated U uptake by V S. alfredii roots at Th10 (10 µM of Th), however, the opposite was observed at Th100 (100 µM of Th). A similar result was found in the effect of U on the uptake of Th by V S. alfredii. Subcellular fractionation studies of V S. alfredii indicated that U and Th were mainly stored in cell wall fraction, and much less was found in organelle and soluble fractions. Chemical form examination results showed that water-soluble U and Th were the predominant chemical forms in this plant. Addition of the other radionuclide in aqueous solutions altered the concentration and percentage of U or Th in cell wall fraction and in water-soluble form, resulting in the change of the uptake capacity of U or Th by V S. alfredii roots. Comparing with single U or Th treatment, the plant cells revealed more swollen chloroplasts and enhanced thickening in cell walls under the U100 + Th100 treatment, as observed by TEM. Those results collectively displayed that V S. alfredii may be utilized as a potential plant to simultaneously remove U and Th from aqueous solutions (rhizofiltration).

Highly efficient extraction of actinides with pillar[5]arene-derived diglycolamides in ionic liquids via a unique mechanism involving competitive host-guest interactions.

Actinide partitioning is considered as one of the most challenging issues in nuclear waste remediation. Herein, we unravel a novel extraction mode pertinent to the competitive host-guest interactions for highly efficient actinide extraction. The host-guest recognition event involves binding of a room temperature ionic liquid (RTIL), 1-n-octyl-3 methylimidazolium bis(trifluoromethane)sulfonamide (C8mimNTf2), as both the guest and the solvent by the hosts pillar[5]arene-based diglycolamides (P5DGAs) and the subsequent displacement of the guest by a metal ion. This two-step process suggests a unique competitive ion-mediated displacement mechanism for the metal ion partitioning in the extraction process. The supramolecular extraction system is evaluated for its extraction abilities towards actinide ions such as UO22+, PuO22+, Pu4+, Am3+, and fission product elements such as Eu3+, Sr2+, Cs+. The results demonstrate the exceedingly high distribution ratios and favorable separation of Am3+ and Pu4+ in nitric acid media. All the three P5DGAs form 1 : 1 complexes with Am3+. Time resolved laser fluorescence spectroscopic (TRLFS) studies reveal a strong complexation involving no inner-sphere water molecules in the Eu3+-P5DGA complexes when C8mimNTf2 is used as the diluent. With high efficiency in the extraction of actinides and a quantitative back extraction outcome, the RTIL-based solvent systems containing pillar[5]arene-DGA ligands developed in this work hold potential as promising candidates for nuclear waste remediation in a more sustainable fashion.

A novel benzimidazole-functionalized 2-D COF material: synthesis and application as a selective solid-phase extractant for separation of uranium.

A novel COF-based material (COF-COOH) containing large amounts of carboxylic groups was prepared for the first time by using a simple and effective one-step synthetic method, in which the cheap and commercially available raw materials, trimesoyl chloride and p-phenylenediamine, were used. The as-synthesized COF-COOH was modified with previously synthesized 2-(2,4-dihydroxyphenyl)-benzimidazole (HBI) by "grafting to" method, and a new solid-phase extractant (COF-HBI) with highly efficient sorption performance for uranium(VI) was consequently obtained. A series of characterizations demonstrated that COF-COOH and COF-HBI exhibited great thermostabilities and irradiation stabilities. Sorption behavior of the COF-based materials toward U(VI) was compared in simulated nuclear industrial effluent containing UO2(2+) and 11 undesired ions, and the UO2(2+) sorption amount of COF-HBI was 81 mg g(-1), accounting for approximately 58% of the total sorption amount, which was much higher than the sorption selectivity of COF-COOH to UO2(2+) (39%). Batch sorption experiment results indicated that the uranium(VI) sorption on COF-HBI was a pH dependent, rapid (sorption equilibrium was reached in 30 min), endothermic and spontaneous process. In the most favorable conditions, the equilibrium sorption capacity of the adsorbent for uranium could reach 211 mg g(-1).

The influence of different hydroponic conditions on thorium uptake by Brassica juncea var. foliosa.

The effects of different hydroponic conditions (such as concentration of thorium (Th), pH, carbonate, phosphate, organic acids, and cations) on thorium uptake by Brassica juncea var. foliosa were evaluated. The results showed that acidic cultivation solutions enhanced thorium accumulation in the plants. Phosphate and carbonate inhibited thorium accumulation in plants, possibly due to the formation of Th(HPO4)(2+), Th(HPO4)2, or Th(OH)3CO3 (-) with Th(4+), which was disadvantageous for thorium uptake in the plants. Organic aids (citric acid, oxalic acid, lactic acid) inhibited thorium accumulation in roots and increased thorium content in the shoots, which suggested that the thorium-organic complexes did not remain in the roots and were beneficial for thorium transfer from the roots to the shoots. Among three cations (such as calcium ion (Ca(2+)), ferrous ion (Fe(2+)), and zinc ion (Zn(2+))) in hydroponic media, Zn(2+) had no significant influence on thorium accumulation in the roots, Fe(2+) inhibited thorium accumulation in the roots, and Ca(2+) was found to facilitate thorium accumulation in the roots to a certain extent. This research will help to further understand the mechanism of thorium uptake in plants.