Anion exchange on hydrous zirconium oxide materials: application for selective iodate removal.

The radioactive I is a top-priority radionuclide due to its the long half-life (1.57 × 10 years) and high mobility. Because of the planned and accidental releases to the environment, specific separation technologies are required to limit the potential radiation dose to human beings.

Application of multi-edge HERFD-XAS to assess the uranium valence electronic structure in potassium uranate (KUO).

The uranium valence electronic structure in the prototypical undistorted perovskite KUO is reported on the basis of a comprehensive experimental study using multi-edge HERFD-XAS and relativistic quantum chemistry calculations based on density functional theory. Very good agreement is obtained between theory and experiments, including the confirmation of previously reported Laporte forbidden f-f transitions and X-ray photoelectron spectroscopic measurements. Many spectral features are clearly identified in the probed U-f, U-p and U-d states and the contribution of the O-p states in those features could be assessed.

Harmonics as an alternative method for measuring I during x-ray absorption spectroscopy experiments at laboratory scale.

In the recent years, the advent of an efficient and compact laboratory-scale spectrometer for x-ray absorption spectroscopy experiments has been extensively reported in the literature. Such modern instruments offer the advantage to routinely use x-ray absorption spectroscopy on systematic studies, which is usually unconceivable at synchrotron radiation source facilities due to often limited time access. However, one limiting factor is the fact that due to laboratory x-ray source brightness compared to a synchrotron, two separate measures of the incoming and transmitted x-ray intensities, i.

Local Structure in U(IV) and U(V) Environments: The Case of UO.

A comprehensive analysis of X-ray absorption data obtained at the U -edge for a systematic series of single-valence (UO, KUO, UO) and mixed-valence uranium compounds (UO, UO, UO) is reported. High-energy resolution fluorescence detection (HERFD) X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) methods were applied to evaluate U(IV) and U(V) environments, and in particular, to investigate the UO local structure. We find that the valence state distribution in mixed-valence uranium compounds cannot be confidently quantified from a principal component analysis of the U -edge XANES data.

Trends in the valence band electronic structures of mixed uranium oxides.

The valence band electronic structures of mixed uranium oxides (UO2, U4O9, U3O7, U3O8, and β-UO3) have been studied using the resonant inelastic X-ray scattering (RIXS) technique at the U M5 edge and computational methods. We show here that the RIXS technique and recorded U 5f-O 2p charge transfer excitations can be used to test the validity of theoretical approximations.

Evolution of the Uranium Chemical State in Mixed-Valence Oxides.

A fundamental question concerning the chemical state of uranium in the binary oxides UO, UO, UO, UO, and UO is addressed. By utilizing high energy resolution fluorescence detection X-ray absorption near edge spectroscopy (HERFD-XANES) at the uranium M edge, a novel technique in the tender X-ray region, we obtain the distribution of formal oxidation states in the mixed-valence oxides UO, UO, and UO. Moreover, we clearly identify a pivot from U(IV)-U(V) to U(V)-U(VI) charge compensation, corresponding with transition from a fluorite-type structure (UO) to a layered structure (UO).

Use of HERFD-XANES at the U L3- and M4-Edges To Determine the Uranium Valence State on [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3].

We report and discuss here the unambiguous uranium valence state determination on the complex compound [Ni(H2O)4]3[U(OH,H2O)(UO2)8O12(OH)3] by using high-energy-resolution fluorescence detection-X-ray absorption near-edge structure spectroscopy (HERFD-XANES). The spectra at both U L3- and M4-edges confirm that all five nonequivalent U atoms are solely in the hexavalent form in this compound, as previously suggested by bond-valence-sum analysis and X-ray diffraction pattern refinement. Moreover, the presence of the preedge feature, due to the 2p3/2-5f quadrupole transition, has been observed in the U L3-edge HERFD-XANES spectrum, in agreement with theoretical and experimental observations of other uranium-based compounds.

New insight into self-irradiation effects on local and long-range structure of uranium-americium mixed oxides (through XAS and XRD).

Uranium-americium mixed oxides could be used as transmutation targets to lower Am inventory in spent nuclear fuels. Due to (241)Am activity, these materials are subjected to α-self-irradiation which provokes crystallographic disorder. Previous studies on U-Am mixed oxides gave first insight into α-radiation tolerance of these compounds, but have never been carried out for more than a year, whereas these compounds might be stored up to a few years between fabrication and irradiation.