Chronicles of plutonium peroxides: spectroscopic characterization of a new peroxo compound of Pu(IV).

Although hydrogen peroxide (H2O2) has been highly used in nuclear chemistry for more than 75 years, the preparation and literature description of tetravalent actinide peroxides remain surprisingly scarce. A new insight is given in this topic through the synthesis and thorough structural characterization of a new peroxo compound of Pu(IV).

Micrometric drilling of (meta-)studtite square platelets formed by pseudomorphic conversion of UO2 under high-frequency ultrasound.

Pseudomorphic transformations are related to chemical conversions of materials while conserving their shape and structural features. Structuring ceramic shapes this way can be used to tailor the physico-chemical properties of materials that can benefit particular applications. In the context of spent nuclear fuel storage interacting with radiolysis products, the sonochemical behavior of powdered UO2 was investigated in dilute aqueous solutions saturated with Ar/(20 %)O2 (20 °C). Optimized parameter settings enabled the complete conversion of UO2 micrometric platelets into uranyl peroxide precipitates, referred to as (meta-)studtite [(UO2(O2)(H2O)2)xH2O] with x = 2 or 4. While the most acidic conditions yielded elongated crystal shapes in agreement with a dissolution/reprecipitation mechanism, softer conditions allowed the pseudomorphic transformation of the platelet shape oxide suggesting a complex formation mechanism. For specific conditions, this unprecedented morphology was accompanied with the formation of a hole in the platelet center. Investigations revealed that the formation of the drilled polymorphs is related to a perfect blend of H+, in-situ generation of H2O2 and high-frequency ultrasound, and is most probably related to the sono-capillary effect. These insights pave the way for new sonochemical approaches dedicated to the preparation of material polymorphs tailoring specific structural properties.

Investigation of the Plutonium(IV) Interactions with Two Variants of the EF-Hand Ca-Binding Site I of Calmodulin.

Due to its presence in the nuclear industry and its strong radiotoxicity, plutonium is an actinide of major interest in the event of internal contamination. To improve the understanding of its mechanisms of transport and accumulation in the body, the complexation of Pu(IV) to the most common protein calcium-binding motif found in cells, the EF-hand motif of calmodulin, was investigated. Visible and X-ray absorption spectroscopies (XAS) in solution made it possible to investigate the speciation of plutonium at physiological pH (pH 7.4) and pH 6 in two variants of the calmodulin Ca-binding site I and using Pu(IV) in different media: carbonate, chloride, or nitrate solutions. Three different species of Pu were identified in the samples, with formation of 1:1 Pu(IV):calmodulin peptide complexes, Pu(IV) reduction, and formation of peptide-mediated Pu(IV) hexanuclear cluster.

Ultrasonically controlled synthesis of UO2+x colloidal nanoparticles.

Actinide colloids and nanoparticles (NPs) currently constitute a topic of strong interest due to their potential role in advanced nuclear energetics and the environmental migration of radioactivity. A better understanding of the physico-chemical properties of nanoscale actinide oxides requires robust synthesis approaches. In this work, UO2+x NPs were successfully prepared by sonochemistry from U(IV) solutions previously stabilised in a hydrochloric medium (20 kHz, 65 °C, Ar/(10%)CO). Colloidal suspensions were found to be composed of crystalline and spherical NPs showing a UO2-like structure and measuring 18.0 ± 0.1 nm (SAXS, HR-TEM and PXRD techniques). In comparison with the controlled hydrolysis approach used as a reference, sonochemistry appears to be a simple and original synthesis route providing larger, better defined and more crystalline UO2+x NPs with a narrower size distribution. These well-defined NPs offer new opportunities for the preparation of reference actinide materials devoted to fundamental, technological and environmental studies.

Synthesis and multi-scale properties of PuO2 nanoparticles: recent advances and open questions.

Due to the increased attention given to actinide nanomaterials, the question of their structure-property relationship is on the spotlight of recent publications. Plutonium oxide (PuO2) particularly plays a central role in nuclear energetics and a comprehensive knowledge about its properties when nanosizing is of paramount interest to understand its behaviour in environmental migration schemes but also for the development of advanced nuclear energy systems underway. The element plutonium further stimulates the curiosity of scientists due to the unique physical and chemical properties it exhibits around the periodic table. PuO2 crystallizes in the fluorite structure of the face-centered cubic system for which the properties can be significantly affected when shrinking. Identifying the formation mechanism of PuO2 nanoparticles, their related atomic, electronic and crystalline structures, and their reactivity in addition to their nanoscale properties, appears to be a fascinating and challenging ongoing topic, whose recent advances are discussed in this review.

First observation of [Pu6(OH)4O4]12+ cluster during the hydrolytic formation of PuO2 nanoparticles using H/D kinetic isotope effect.

New insights are provided about the formation mechanism of PuO2 nanoparticles (NPs) by investigating an unprecedented kinetic isotope effect observed during their hydrolytic synthesis in H2O or D2O and attributed to OH/OD zero point energy difference. The signature of a Pu(IV) oxo-hydroxo hexanuclear cluster, appearing as an important intermediate during the formation of the 2 nm PuO2 NPs (synchrotron SAXS/XAS), is further revealed indicating that their formation is controlled by H-transfer reactions occurring during hydroxo to oxo-bridge conversions.

Contribution of Molecular Dynamics in pNMR for the Structural Determination of AnV and AnVI Complexes in Solution.

In this study, we propose to use classical molecular dynamics (MD) coupled with 1H NMR spectroscopy to study the conformations of different actinyl AnVI (An = U, Np, and Pu) and AnV (An = Np) complexes with tetra-ethyl dyglicolamide (TEDGA) ligands in order to have a better representation of such complexes in solution. Molecular dynamics simulations showed its effectiveness in interpreting the experiments by the calculation of geometric factors needed for the determination of magnetic properties of these complexes. We demonstrated that different conformations of the AnV and AnVI complexes with TEDGA exist in solution with different coordination modes, which is experimentally confirmed by 1H NMR and EXAFS spectroscopies. Furthermore, MD simulations provide additional insights into the structures of complexes in solution since conformations with fast exchanges, which are not accessible from NMR experiments, have been observed by MD simulations.

Correction: Formation of plutonium(IV) silicate species in very alkaline reactive media.

Correction for 'Formation of plutonium(IV) silicate species in very alkaline reactive media' by Paul Estevenon et al., Dalton Trans., 2021, 50, 12528-12536, DOI: 10.1039/D1DT02248B.

Characterization of a Hexanuclear Plutonium(IV) Nanostructure in an Acetate Solution via Visible-Near Infrared Absorption Spectroscopy, Extended X-ray Absorption Fine Structure Spectroscopy, and Density Functional Theory.

A new hexanuclear plutonium cluster has been stabilized in aqueous media with acetate ligands. To probe the formation of such a complex structure, visible-near infrared (vis-NIR) absorption spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) were combined. The presence of Pu6O4(OH)4(CH3COO)12 species in solution was first detected by vis-NIR and EXAFS spectroscopy. To confirm unambiguously this structure, EXAFS spectra were simulated from ab initio calculations. Debye-Waller factors and structural parameters were derived from DFT calculations. A large number of 5f electrons were treated as valence or core electrons using small- and large-core relativistic effective pseudopotentials. It is possible to reproduce accurately the EXAFS spectrum of the octahedral hexamer cluster at both levels of calculations. Further DFT and EXAFS calculations were performed on clusters of lower or higher nuclearities and of different geometries using the 5f-core approximation. The result shows that trimer, tetramer, flat hexamer, and even 16-mer clusters exhibit different EXAFS patterns and confirm the very specific octahedral hexanuclear EXAFS signature.

X-ray absorption spectroscopy and actinide electrochemistry: a setup dedicated to radioactive samples applied to neptunium chemistry.

A spectroelectrochemical setup has been developed to investigate radioactive elements in small volumes (0.7 to 2 ml) under oxidation-reduction (redox) controlled conditions by X-ray absorption spectroscopy (XAS). The cell design is presented together with in situ XAS measurements performed during neptunium redox reactions. Cycling experiments on the NpO22+/NpO2+ redox couple were applied to qualify the cell electrodynamics using XANES measurements and its ability to probe modifications in the neptunyl hydration shell in a 1 mol l-1 HNO3 solution. The XAS results are in agreement with previous structural studies and the NpO22+/NpO2+ standard potential, determined using Nernst methods, is consistent with measurements based on other techniques. Subsequently, the NpO2+, NpO22+ and Np4+ ion structures in solution were stabilized and measured using EXAFS. The resulting fit parameters are again compared with other results from the literature and with theoretical models in order to evaluate how this spectroelectrochemistry experiment succeeds or fails to stabilize the oxidation states of actinides. The experiment succeeded in: (i) implementing a robust and safe XAS device to investigate unstable radioactive species, (ii) evaluate in a reproducible manner the NpO22+/NpO2+ standard potential under dilute conditions and (iii) clarify mechanistic aspects of the actinyl hydration sphere in solution. In contrast, a detailed comparison of EXAFS fit parameters shows that this method is less appropriate than the majority of the previously reported chemical methods for the stabilization of the Np4+ ion.

Size and structure of hexanuclear plutonium oxo-hydroxo clusters in aqueous solution from synchrotron analysis.

The size and shape of a water-soluble hexanuclear plutonium cluster were probed by combining synchrotron small-angle X-ray scattering (SAXS) and extended X-ray absorption fine structure (EXAFS). A specific setup coupling both techniques and dedicated to radioactive samples on the MARS beamline endstation at Synchrotron SOLEIL is described. The plutonium hexanuclear cores are well stabilized by the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid ligands and this allows a good evaluation of the setup to probe the very small plutonium core. The results show that, in spite of the constrained conditions required to avoid any risk of sample dispersion, the flux and the sample environment are optimized to obtain a very good signal-to-noise ratio, allowing the detection of small plutonium aggregates in an aqueous phase. The structure of the well defined hexanuclear cluster has been confirmed by EXAFS measurements in solution and correlated with SAXS data processing and modelling. An iterative comparison of classical fit models (Guinier or sphere form factor) with the experimental results allowed a better interpretation of the SAXS signal that will be relevant for future work under environmentally relevant conditions.

Formation of plutonium(IV) silicate species in very alkaline reactive media.

Studying the speciation of Pu(IV) in very alkaline and silicate ion rich reactive media allowed identification of the formation of plutonium(IV)-silicate colloidal suspensions which were stable for months. These colloids were stabilized in aqueous solution for pH > 13 and for concentrations around 10-2 mol L-1. Successive filtration processes allowed evaluation of their size, which was found to be smaller than 6 nm. Their structural characterization by XAS evidenced that their structure was similar to those identified for the other tetravalent actinide-silicate colloidal systems like thorium, uranium and neptunium. Their formation could explain the increase of plutonium solubility usually observed in alkaline silicate-rich solutions and could affect the plutonium mobility as a result in contaminated sites or in other environmental permeable media.

Ultrasonically assisted conversion of uranium trioxide into uranium(vi) intrinsic colloids.

Under oxidizing conditions, the corrosion of spent nuclear fuel may lead to the leaching of radionuclides including soluble uranyl-based species. The speciation of the generated chemical forms is complex and the related potential formation of colloidal species appears surprisingly poorly reported in the literature. Their formation could however contribute significantly to the mobility of radionuclides in the environment. A better knowledge in the speciation and reactivity of these species appears particularly relevant. This study describes the preparation and characterization of intrinsic uranium(vi) colloids from amorphous and crystalline UO3 in pure water assisted by 20 kHz ultrasound. In the presence of carbon monoxide preventing the sonochemical formation of hydrogen peroxide, ultrasonic treatment boosts the conversion of UO3 powder into (meta-)schoepite precipitates and yields very stable and notably concentrated uranium(vi) nanoparticles in the liquid phase. Using HR-TEM, SAXS and XAS techniques, we confirmed that the colloidal suspension is composed of quasi-spherical nanoparticles measuring ca. 3.8 ± 0.3 nm and exhibiting a schoepite-like crystallographic structure. The proposed method demonstrates the possible formation of environmentally relevant U(vi) colloidal nanoparticles appearing particularly interesting for the preparation of reference systems in the absence of added ions and capping agents.

A 70-Year-Old Mystery in Technetium Chemistry Explained by the New Technetium Polyoxometalate [H7 O3 ]4 [Tc20 O68 ] ⋠4H2 O.

[H7 O3 ]4 [Tc20 O68 ] ⋅ 4H2 O [1] was prepared from an aqueous Tc2 O7 solution concentrated over anhydrous H2 SO4 . [Tc20 O68 ]4- is the first polyanionic species to be reported for Tc. The unit cell contains one centrosymmetric [Tc20 O68 ]4- polyanion as well as hydronium ions and water molecules. The core of the structure consists of four Tc(V)O6 octahedra that form a square Tc4 O4 ring. The four Tc(V)O6 octahedra are decorated by sixteen Tc(VII)O4 tetrahedra. Calculations show the bonding within the Tc4 O4 ring to consist of a 3-center bond formed between each neighboring pair of Tc atoms and their bridging oxygen. Calculations also indicate that a strong d→d electronic transition at 513 nm is the origin of the red color of [1]. The characterization of red HTcO4 solutions by X-ray absorption spectroscopy has complemented the description of this compound in aqueous solution. The formation mechanisms in solution, including the possible role of technetium's radioactivity in the formation of [1], are discussed.

Electrochemical and Spectroscopic Study of EuIII and EuII Coordination in the 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid.

Separation processes based on room temperature ionic liquids (RTIL) and electrochemical refining are promising strategies for the recovery of lanthanides from primary ores and electronic waste. However, they require the speciation of dissolved elements to be known with accuracy. In the present study, Eu coordination and EuIII /EuII electrochemical behavior as a function of water content in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2 ]) was investigated using UV-visible spectrophotometry, time-resolved laser fluorescence spectroscopy, electrochemistry, and X-ray absorption spectroscopy. In situ measurements were performed in spectroelectrochemical cells. Under anhydrous conditions, EuIII and EuII were complexed by NTf2 , forming Eu-O and Eu-(N,O) bonds with the anion sulfoxide function and N atoms, respectively. This complexation resulted in a greater stability of EuII , and in quasi-reversible oxidation-reduction with an E0 ' potential of 0.18 V versus the ferrocenium/ferrocene (Fc+ /Fc) couple. Upon increasing water content, progressive incorporation of water in the EuIII coordination sphere occurred. This led to reversible oxidation-reduction reactions, but also to a decrease in stability of the +II oxidation state (E0 '=-0.45 V vs. Fc+ /Fc in RTIL containing 1300 mm water).

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.

Probing the local structure of nanoscale actinide oxides: a comparison between PuO2 and ThO2 nanoparticles rules out PuO2+x hypothesis.

Actinide research at the nanoscale is gaining fundamental interest due to environmental and industrial issues. The knowledge of the local structure and speciation of actinide nanoparticles, which possibly exhibit specific physico-chemical properties in comparison to bulk materials, would help in a better and reliable description of their behaviour and reactivity. Herein, the synthesis and relevant characterization of PuO2 and ThO2 nanoparticles displayed as dispersed colloids, nanopowders, or nanostructured oxide powders allow to establish a clear relationship between the size of the nanocrystals constituting these oxides and their corresponding An(iv) local structure investigated by EXAFS spectroscopy. Particularly, the first oxygen shell of the probed An(iv) evidences an analogous behaviour for both Pu and Th oxides. This observation suggests that the often observed and controversial splitting of the Pu-O shell on the Fourier transformed EXAFS signal of the PuO2 samples is attributed to a local structural disorder driven by a nanoparticle surface effect rather than to the presence of PuO2+x species.

Formation of CeSiO4 from cerium(iii) silicate precursors.

Although the preparation of CeSiO4 has been already reported, the formation of pure cerium silicate from aqueous precursors appears as a challenge. An innovative way of synthesis has been identified in this study, allowing the formation of CeSiO4 after hydrothermal treatment starting from Ce(iii) silicate precursors. Among the experimental parameters examined, significant effects were found according to the nature of the precursor and of the reactive media considered, the pH of the reactive media and the temperature of the hydrothermal process. This study allows the determination of optimized conditions for the hydrothermal synthesis of pure CeSiO4 (A-Ce2Si2O7 or Ce4.67(SiO4)3O as starting precursors, nitric medium, pH = 7, 7 days at 150 °C). The in situ low oxidation rate of Ce(iii) into Ce(iv) was a key parameter to consider in order to avoid the presence of CeO2 in the final mixtures.

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.

Deciphering the Crystal Structure of a Scarce 1D Polymeric Thorium Peroxo Sulfate.

The preparation and structural characterization of an original Th peroxo sulfate dihydrate, crystallizing at room temperature in the form of stable 1D polymeric microfibres is described. A combination of laboratory and synchrotron techniques allowed solution of the structure of the Th(O2 )(SO4 )(H2 O)2 compound, which crystallizes in a new structure type in the space group Pna21 of the orthorhombic crystal system. Particularly, the peroxide ligand coordinates to the Th cations in an unusual µ3 -η2 :η2 :η2 bridging mode, forming an infinite 1D chain decorated with sulfato ligands exhibiting simultaneously monodentate and bidentate coordination modes.