Aggregation of Bifunctional Extractants Used for Uranium(VI) Separation.

DEHCNPB (butyl-N,N-di(2-ethylhexyl)carbamoyl-nonylphosphonate) is an amido-phosphonic acid that has remarkable properties for the separation of uranium from wet phosphoric acid. Despite previous studies, a detailed description of the DEHCNPB organic solutions at the supramolecular and molecular scales is missing. In the present work, we use classical Molecular Dynamics (MD) combined with SANS and SAXS experimental data in order to describe the aggregation of the bifunctional extractant DEHCNPB as well as the speciation of uranium(VI) in such systems. We provide a fine description of the molecular species in the organic solution and of the interactions within the aggregates formed, shedding light on solvent extraction mechanisms. Without uranium, the organic phase is highly composed of dimers and trimers H-bonded through phosphonate functions and without water molecules. With uranium, two to three extractant molecules coordinate directly the uranyl cation by their phosphonate groups. Uranyl is not fully dehydrated in this organic solution, and the amide groups of the extractants are found to form H-bonds with the water molecules bound to uranyl. These H-bond networks around the metallic cation stabilize the complexes and facilitate the extraction. These results underline the importance of considering weak interactions in the understanding of extraction processes and demonstrate how molecular simulations provide essential insights into such complex organic phase chemistry with a high number of species.

Insights from quantum chemical calculations into inner and outer-sphere complexation of plutonium(IV) by monoamide and carbamide extractants.

The strong influence of the structure of amide derivatives on their extraction properties has been demonstrated in several studies in the literature. To investigate and rationalize the influence of the nature and length of the monoamide alkyl chains on Pu(iv) extraction/complexation, a theoretical study was performed using the Density Functional Theory (DFT) method in the scalar relativistic framework. For that, the geometries for the inner/outer-sphere complexes and interaction energies of [Pu(NO3)4] and [Pu(NO3)6]2- with different ligands have been calculated. For both inner and outer-sphere complexes, it is found that the introduction of a bulky alkyl group on the carbonyl side strongly diminishes the complexation energy. This is fully consistent with monamide extraction properties. The influence of the bulkiness of the alkyl group is as or even more important for outer than for inner-sphere interactions. This result was unexpected when considering that there are less flexibility and stronger steric constraints in the inner sphere compared to the outer one. However, this can be attributed to specific electrostatic interactions between the two outer-sphere amide ligands and two nitrate ions of [Pu(NO3)6]2-. By increasing the polarity of the solution, such interactions diminish and the outer-sphere ligands move away from [Pu(NO3)6]2-. Consequently, the solvent effects were found to be very significant for outer-sphere complexation while rather small for inner-sphere complexation. This gives the key possibility to tune the substituent effect by changing the polarity of the solution. As for carbamide ligands, it was found that the weak interactions (dispersion) have remarkable effects on both inner and outer-sphere complexations.

Temperature Dependence of 1 H Paramagnetic Chemical Shifts in Actinide Complexes, Beyond Bleaney's Theory: The AnVI O2 2+ -Dipicolinic Acid Complexes (An=Np, Pu) as an Example.

Actinide +VI complexes ( A n V I = U V I , N p V I and P u V I ) with dipicolinic acid derivatives were synthesized and characterized by powder XRD, SQUID magnetometry and NMR spectroscopy. In addition, N p V I and P u V I complexes were described by first principles CAS based and two-component spin-restricted DFT methods. The analysis of the 1 H paramagnetic NMR chemical shifts for all protons of the ligands according to the X-rays structures shows that the Fermi contact contribution is negligible in agreement with spin density determined by unrestricted DFT. The magnetic susceptibility tensor is determined by combining SQUID, pNMR shifts and Evans' method. The SO-RASPT2 results fit well the experimental magnetic susceptibility and pNMR chemical shifts. The role of the counterions in the solid phase is pointed out; their presence impacts the magnetic properties of the N p V I complex. The temperature dependence of the pNMR chemical shifts has a strong 1 / T contribution, contrarily to Bleaney's theory for lanthanide complexes. The fitting of the temperature dependence of the pNMR chemical shifts and SQUID magnetic susceptibility by a two-Kramers-doublet model for the N p V I complex and a non-Kramers-doublet model for the P u V I complex allows for the experimental evaluation of energy gaps and magnetic moments of the paramagnetic center.

Coordination Structures of Uranium(VI) and Plutonium(IV) in Organic Solutions with Amide Derivatives.

Carbamide and monoamide derivatives are very promising molecules to achieve U(VI) and Pu(IV) extraction and separation from spent nuclear fuels through solvent extraction. Herein, coordination structures of U(VI) and Pu(IV) complexes with carbamide derivatives were characterized using X-ray crystallography as well as infrared, UV-visible, and EXAFS spectroscopies. Coordination structures are compared to those obtained for monoamide derivatives in order to better understand the role of coordination chemistry in extraction properties. Single crystals were first synthesized with a short alkyl chain carbamide analog. Carbamide complexation in the solid state is found analogous to that in the monoamide. In organic solution, upon solvent extraction from nitric acid aqueous solution, it is shown that both amide derivatives can bind in the inner and outer coordination spheres of uranium(VI) and plutonium(IV). The amount of outer sphere coordination complexes increases with the amount of nitric acid. With uranium(VI), at a nitric acid concentration up to 5 mol·L-1, amide derivatives operate predominantly in the inner coordination sphere. In contrast, Pu(IV) coordination geometry is much more sensitive toward acid concentration or ligand structure than U(VI). Pu(IV) changes from inner sphere complexation at 0.5 mol·L-1 HNO3 to mostly outer sphere complexation at 4 mol·L-1. The proportion of outer-sphere complexes is strongly influenced by the ligand structure. Higher Pu(IV) extraction is found to be correlated with the amount of Pu(IV) outer sphere species. Secondary interactions in the outer sphere coordination shell appear to be of primary importance for plutonium extraction.

Properties of the tetravalent actinide series in aqueous phase from a microscopic simulation self-consistent engine.

In the context of nuclear fuel recycling and environmental issues, the understanding of the properties of radio-elements with various approaches remains a challenge regarding their dangerousness. Moreover, experimentally, some issues are also of importance; first, it is imperative to work at sufficiently high concentrations to reach the sensitivities of the analytical tools, however this condition often leads to precipitation for some of them; second, stabilizing specific oxidation states of some actinides remains a challenge, thus making it difficult to extract general trends across the actinide series. Complementary to experiments, modeling can be used to unbiasedly probe the actinide's properties in an aquatic environment and offers a predictive tool. We report the first molecular dynamics simulations based on homogeneously built force fields for the whole series of the tetravalent actinides in aqueous phase from ThIV to BkIV and including PuIV. The force fields used to model the interactions among the constituents include polarization and charge donation microscopic effects. They are built from a self-consistent iterative ab initio based engine that can be included in future developments as an element of a potential machine learning procedure devoted to generating accurate force fields. The comparison of our simulated hydrated actinide properties to available experimental data shows the model robustness and the relevance of our parameter assignment engine. Moreover, our simulated structural, dynamical and evolution of the hydration free energy data show that, apart from AmIV and CmIV, the actinide properties change progressively along the series.

Inner to outer-sphere coordination of plutonium(iv) with N,N-dialkyl amide: influence of nitric acid.

N,N-Dialkylamides are extensively studied as alternative organic ligands to achieve the extraction and separation of uranium(vi) and plutonium(iv). We report here the coordination structures of the plutonium(iv) ion with N,N-di(2-ethylhexyl)-n-butanamide as a function of nitric acid concentration in the aqueous phase. The coordination structure of Pu(iv) evolves gradually with increasing nitric acid concentration from an inner-sphere with two coordinated amide ligands toward an outer-sphere hexanitrate complex with only nitrate ions in the first coordination sphere and protonated amide ligands in the outer shell.

Structures of Plutonium(IV) and Uranium(VI) with N,N-Dialkyl Amides from Crystallography, X-ray Absorption Spectra, and Theoretical Calculations.

The structures of plutonium(IV) and uranium(VI) ions with a series of N,N-dialkyl amides ligands with linear and branched alkyl chains were elucidated from single-crystal X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and theoretical calculations. In the field of nuclear fuel reprocessing, N,N-dialkyl amides are alternative organic ligands to achieve the separation of uranium(VI) and plutonium(IV) from highly concentrated nitric acid solution. EXAFS analysis combined with XRD shows that the coordination structure of U(VI) is identical in the solution and in the solid state and is independent of the alkyl chain: two amide ligands and four bidentate nitrate ions coordinate the uranyl ion. With linear alkyl chain amides, Pu(IV) also adopt identical structures in the solid state and in solution with two amides and four bidentate nitrate ions. With branched alkyl chain amides, the coordination structure of Pu(IV) was more difficult to establish unambiguously from EXAFS. Density functional theory (DFT) calculations were consequently performed on a series of structures with different coordination modes. Structural parameters and Debye-Waller factors derived from the DFT calculations were used to compute EXAFS spectra without using fitting parameters. By using this methodology, it was possible to show that the branched alkyl chain amides form partly outer-sphere complexes with protonated ligands hydrogen bonded to nitrate ions.