Molecular and Supramolecular Study of Uranium/Plutonium Liquid-Liquid Extraction with N,N-Dialkylamides.

In the context of the separation of uranium and plutonium from spent fuel allowed by N,N-dialkylamides, three regioisomers of N,N-di(2-ethylhexyl) butyramide (DEHBA or ßß) and the diastereopure isomers of N-(2-ethylhexyl)-N-(oct-3-yl)butyramide (EHOBA or αß) were synthesized to assess their extraction performance and to study the mechanisms at the origin of the differences observed between the stereo- and regioisomers. The N,N-dialkylamides showed differences in extraction, with a greater effect of regio- than stereoisomerism. A mechanistic study at both the molecular and supramolecular scales was initially applied to explain these effects. X-ray absorption and UV-vis spectroscopy showed that uranium is extracted by a UO2(NO3)2L2 complex, which is not very sensitive to steric hindrance, while plutonium is extracted by two complexes, Pu(NO3)4L2 and Pu(NO3)6(HL)2, which are differently affected by stereo- and regioisomerism. Investigations at the supramolecular scale also showed that Pu(NO3)4L2 complexes are disadvantaged by the bulkiness of the extractants, while Pu(NO3)6(HL)2 is favored by the preformation of larger supramolecular aggregates.

New Carbamoyl Surface-Modified ZrO2 Nanohybrids for Selective Au Extraction from E-Waste.

Efficient and selective extractions of precious and critical metal ions such as Au(III) and Pd(II) were investigated using zirconia nanoparticles surface modified with different organic mono- and di-carbamoyl phosphonic acid ligands. The modification is made on the surface of commercial ZrO2 that is dispersed in aqueous suspension and was achieved by optimizing the Bronsted acid-base reaction in ethanol/H2O solution (1:2), resulting in inorganic-organic systems of ZrO2-Ln (Ln: organic carbamoyl phosphonic acid ligand). The presence, binding, amount, and stability of the organic ligand on the surface of zirconia nanoparticles were confirmed by different characterizations such as TGA, BET, ATR-FTIR, and 31P-NMR. Characterizations showed that all the prepared modified zirconia had a similar specific surface area (50 m2.g-1) and the same amount of ligand on the zirconia surface in a 1:50 molar ratio. ATR-FTIR and 31P-NMR data were used to elucidate the most favorable binding mode. Batch adsorption results showed that (i) ZrO2 surface modified with di-carbamoyl phosphonic acid ligands had the highest adsorption efficiency to extract metals than mono-carbamoyl ligands, and (ii) higher hydrophobicity of the ligand led to better adsorption efficiency. The surface-modified ZrO2 with di-N,N-butyl carbamoyl pentyl phosphonic acid ligand (ZrO2-L6) showed promising stability, efficiency, and reusability in industrial applications for selective gold recovery. In terms of thermodynamic and kinetic adsorption data, ZrO2-L6 fits the Langmuir adsorption model and pseudo-second-order kinetic model for the adsorption of Au(III) with maximum experimental adsorption capacity qmax = 6.4 mg.g-1.

Impact of Solvent Structuring in Water/ tert-Butanol Mixtures on the Assembly of Silica Nanoparticles to Aerogels.

Soft matter structuring is a useful tool for the preparation of well-structured inorganic materials. Here, we report a strategy using a structured solvent based on binary mixtures as a directing agent for silica nanoparticles in aerogel elaboration. Binary mixtures involving water/ethanol and water/ tert-butanol have been respectively chosen as representatives of unstructured and structured solvents. The water/alcohol/TEOS systems were effectively characterized as surfactant-free microemulsions. The enhanced solvent structuring, however, disappears upon the reaction with TEOS, and assembly is directed by solvent structuring found in the binary mixtures. For the first time, the influence of solvent composition on the sol-gel reaction was investigated with respect to the reaction rate and the structuring behavior thanks to dynamic light scattering (DLS), small- and wide-angle X-ray scattering (SWAXS), and transmission electron microscopy (TEM) experiments. The silica nanoparticles aggregate in a different manner depending on the solvent composition, which allows the change in the morphology, the degree of interconnection, and the surface area of the resulting material. Silica nanoparticles with a very high surface area of up to 2000 m2/g can be obtained by this approach.

Tuning the Nanostructure of Highly Functionalized Silica Using Amphiphilic Organosilanes: Curvature Agent Effects.

The self-assembly of amino-undecyl-triethoxysilane (AUT) as micelles in water is considered. The behavior of acid/AUT systems is governed by a complete proton transfer from the acid to the amine, leading to the formation of an ammonium headgroup. This moiety is responsible for the bending of the interface between the organic core of the micelles and the surrounding water. By playing with the size of the acid used as curvature agent, the amphiphilic behavior of the organosilane molecule may be adjusted. We follow the aggregation as the curvature agent size increases. This approach constitutes an efficient and original method in order to tune the nanostructure of highly functionalized silica at the early stage of the elaboration. Small-angle X-ray scattering, wet scanning transmission electron microscopy, dynamic light scattering, and complementary characterization techniques indicate that hybrid organic-inorganic planar objects and vesicles are obtained for smaller curvature agents. Increasing the size of the curvature agent results in a transition of the aggregation geometry from vesicles to cylindrical direct micelles, finally leading to nanofibers organized in a 2D hexagonal network resembling a "reverse MCM-41 structure". A geometrical molecular self-assembly model is finally proposed, considering the dimensions of the surfactant tail and those of the head groups.

Zirconium(IV)-Benzene Phosphonate Coordination Polymers: Lanthanide and Actinide Extraction and Thermal Properties.

Coordination polymers with different P/(Zr + P) molar ratios were prepared by combining aqueous solutions of Zr(IV) and benzenephosphonate derivatives. 1,3,5-Benzenetrisphosphonic acid (BTP) as well as phosphonocarboxylate derivatives in which carboxylate substitutes one or two of the phosphonate groups were chosen as the building blocks. The precipitates obtained on combining the two solutions were not X-ray amorphous but rather were indicative of poorly ordered materials. Hydrothermal treatment did not alter the structure of the materials produced but did result in improved crystalline order. The use of HF as a mineralizing agent during hydrothermal synthesis resulted in the crystallization of at least three relatively crystalline phases whose structure could not be determined owing to the complexity of the diffraction patterns. Gauging from the similarity of the diffraction patterns of all the phases, the poorly ordered precipitates and crystalline materials appeared to have similar underlying structures. The BTP-based zirconium phosphonates all showed a higher selectivity for lanthanides and thorium compared with cations such as Cs(+), Sr(2+), and Co(2+). Substitution of phosphonate groups by carboxylate groups did little to alter the pattern of selectivity implying that selectivity in the system was entirely determined by the -POH group with little influence from the -COOH groups. Samples with the highest phosphorus content showed the highest extraction efficiencies for lanthanide elements, especially the heavy lanthanides such as Dy(3+) and Ho(3+) with separation factors of around four with respect to La(3+). In highly acid solutions (4 M HNO3) there was a pronounced variation in extraction efficiency across the lanthanide series. In situ, nonambient diffraction was performed on ZrBTP-0.8 loaded with Th, Ce, and a complex mixture of lanthanides. In all cases the crystalline Zr2P2O7 pyrophosphate phase was formed at ∼800 °C demonstrating the versatility of this structure.

Bis-Catecholamide-Based Materials for Uranium Extraction.

This work reports the synthesis of formo-phenolic resins containing four catecholamide (CAM) moieties with admixture of phenol, catechol or resorcinol. These chelating resins have been developed to selectively extract U(VI) from seawater. This media is a challenging environment due to a pH around 8.2 and a large excess of alkaline and earth-alkaline cations. From the various sorption experiments investigated, the results indicate that the synthesized material exhibit good sorbent properties for U(VI) with uptake capacity about 50 mg/g for the more promising resins with a pronounced selectivity for uranium even under saline conditions. Thermodynamic and kinetic adsorption data were determined for the best resin (Langmuir adsorption model and pseudo-second order model).

Bis-Catecholamide-Based Materials for Uranium Extraction.

Invited for this month's cover is the collaborating group of Dr Guilhem Arrachart and Dr Stéphane Pellet-Rostaing at Institut de Chimie Séparative de Marcoule (ICSM). The cover picture shows a person going uranium fishing thanks to the use of bis-catecholamide materials. These materials have shown interesting performance for the recovery of uranium in saline environments such as seawater. More information can be found in the Research Article by G. Arrachart, S. Pellet-Rostaing, and co-workers.

Investigation on the vibrational and structural properties of a self-structured bridged silsesquioxane.

The crystalline structure of ureidopyrimidinone-based silane (UPY) has been determined. The local and long range order structuring of the bridged silsesquioxane (MUPY) resulting from the sol-gel hydrolysis-condensation of the former precursor has been investigated by MFTIR (Mid Fourier Transform InfraRed) combined with DFT (Density Functional Theory) and XRD (X-ray diffraction) studies. These studies showed that a long range structuring exists within the organic fragments with the transcription of the DDAA (Donor-Donor-Acceptor-Acceptor) H-bonding array from UPY to MUPY whereas a disordered siloxane network was revealed in the hybrid material.

Terephthalaldehyde-Phenolic Resins as a Solid-Phase Extraction System for the Recovery of Rare-Earth Elements.

Rare-earth elements (REEs) are involved in most high technology devices and have become critical for many countries. The progress of processes for the extraction and recovery of REEs is therefore essential. Liquid-solid extraction methods are an attractive alternative to the conventional solvent extraction process used for the separation and/or purification of REEs. For this purpose, a solid-phase extraction system was investigated for the extraction and valorization of REEs. Ion-exchange resins were synthesized involving the condensation of terephthalaldehyde with resorcinol under alkaline conditions. The terephthalaldehyde, which is a non-hazardous aromatic dialdehyde, was used as an alternative to formaldehyde that is toxic and traditionally involved to prepare phenolic ion-exchange resins. The resulting formaldehyde-free resole-type phenolic resins were characterized and their ion-exchange capacity was investigated in regard to the extraction of rare-earth elements. We herein present a promising formaldehyde and phenol-free as a potential candidate for solid-liquid extraction REE with a capacity higher than 50 mg/g and the possibility to back-extract the REEs by a striping step using a 2 M HNO3 solution.

Silylated melamine and cyanuric acid as precursors for imprinted and hybrid silica materials with molecular recognition properties.

Two monotrialkoxysilylated compounds that consist of complementary fragments of melamine (M) and cyanuric acid (CA) have been synthesised. The molecular recognition properties of the M and CA fragments through complementary hydrogen bonds (DAD and ADA; D=donor, A=acceptor) are the key factor used to direct the formation of hybrid silica materials by using a sol-gel process. These materials were synthesised following two methods: First, an organo-bridged silsesquioxane was obtained by the hydrolysis of the two complementary monotrialkoxysilylated melamine and cyanuric acid derivatives, with fluoride ions as a catalyst. The hydrogen-bonding interactions between the two organic fragments are responsible for the formation of the bridging unit. The transcription of the assembly into the hybrid material was characterised and evidenced by solid-state NMR (29Si, 13C) and FTIR spectroscopic experiments. Second, the molecular recognition was exploited to synthesise an imprinted hybrid silica. This material was prepared by co-condensation of tetraethyl orthosilicate (TEOS) with the monosilylated cyanuric acid derivative (CA) templated by nonsilylated melamine. The melamine template was completely removed by treating the solid material with hydrochloric acid. The reintroduction of the template was performed by treating the resulting material with an aqueous suspension of melamine. These steps were monitored and analysed by several techniques, such as solid-state NMR (29Si, 13C) and FTIR spectroscopic analysis and nitrogen adsorption-desorption isotherms.

Nanostructuring of hybrid silicas through a self-recognition process.

The hydrolysis and condensation of a silylated derivative of ureidopyrimidinone led to nanostructured hybrid silica, such as that depicted, as clearly shown by powder XRD studies. The nanostructuring was directly related to molecular recognition through hydrogen bonding. By combining FTIR, solution and solid-state NMR spectroscopic data, the transcription of the hydrogen-bonding networks from the precursor to the final product was clearly evidenced.

Probing the existence of uranyl trisulfate structures in the AMEX solvent extraction process.

Knowledge of the complex microstructure in solvent extraction phases is mandatory for a full comprehension of ionic separation. Coupling EXAFS with MD simulations for uranyl extraction in sulfuric media with tertiary amine extractants enabled unravelling of the unprecedented uranyl tri-sulfate structure.

Actinide and Lanthanide Adsorption onto Hierarchically Porous Carbons Beads: A High Surface Affinity for Pu.

Structured carbon adsorbents were prepared by carbonizing macroporous polyacrylonitrile beads whose pores were lined with a mesoporous phenolic resin. After activation, the beads were tested for minor actinide (Np and Am), major actinide (Pu and U) and lanthanide (Gd) adsorption in varying acidic media. The activation of the carbon with ammonium persulfate increased the surface adsorption of the actinides, while decreasing lanthanide adsorption. These beads had a pH region where Pu could be selectively extracted. Pu is one of the longest lived, abundant and most radiotoxic components of spent nuclear fuel and thus, there is an urgent need to increase its security of storage. As carbon has a low neutron absorption cross-section, these beads present an affordable, efficient and safe means for Pu separation from nuclear waste.

N-Alkyl calix[4]azacrowns for the selective extraction of uranium.

The selective extraction of uranium by N-octylcalix[4]azacrown (NOCAC) and N-ethylhexylcalix[4]azacrown (NEHCAC) was investigated. The ligands were synthesised in three steps through the functionalisation of t-butyl calix[4]arene at the distal-1,3-positions of the lower rim with ethyl acetate groups followed by cyclisation with (imino)bis(ethane-2,1-diyl)diamide. A detailed investigation on the effect of various parameters, such as the aqueous phase acidity (sulfuric acid), the ionic strength, and ligand concentration, on the extraction of uranium(vi) has been conducted. The effect of the H2SO4 concentration has been studied from 0.02 to 3 M. Preliminary studies carried out on NOCAC in dodecane/octanol diluents showed that the uranium extraction from sulfuric acid is more efficient at a low H2SO4 concentrations. The stoichiometry of complexation was estimated from the slope method, NMR titration, and electrospray ionisation-mass spectrometry analysis. Both ligands were found to be highly selective for uranium(vi) over other competitive cations present in a simulated leach solution containing seven competitive cations. The successful recovery of the uranium from the organic phase has been performed thanks to stripping steps involving ammonium oxalate, ammonium carbonate, and sodium carbonate as stripping agents.