Optimisation of accurate rutile TiO2TiO_2 (110), (100), (101) and (001) surface models from periodic DFT calculations

In this paper, geometric bulk parameters, bulk moduli, energy gaps and relative stabilities of the TiO2 anatase and rutile phases were determined from periodic DFT calculations. Then, for the rutile phase, structures, relaxations and surface energies of the (110), (100), (101) and (001) faces were computed. The calculated surface energies are consistent with the natural rutile powder composition, even if a dependence on the number of layers of the slab used to model the surface was identified. Internal constraints, consisting in freezing some internal layers of the slab to atomic bulk positions, were thus added to mimic the bulk hardness in order to stabilise the computed surface energies for thinner systems. In parallel, the influence of pseudopotentials was studied and it appears that four valence electrons for titanium atoms are sufficient. The aim of this study was to optimise accurate rutile TiO2 surface models that will be used in further calculations to investigate water and uranyl ion sorption mechanisms

Combined investigation of water sorption on TiO2TiO_2 rutile (1 1 0) single crystal face: XPS vs. periodic DFT

XPS and periodic DFT calculations have been used to investigate water sorption on the TiO2 rutile (1 1 0) face. Two sets of XPS spectra were collected on the TiO2 (1 1 0) single crystal clean and previously exposed to water: the first set with photoelectrons collected in a direction parallel to the normal to the surface; and the second set with the sample tilted by 70°, respectively. This tilting procedure promotes the signals from surface species and reveals that the first hydration layer is strongly coordinated to the surface and also that, despite the fact that the spectra were recorded under ultra-high vacuum, water molecules subsist in upper hydration layers. In addition, periodic DFT calculations were performed to investigate the water adsorption process to determine if molecular and/or dissociative adsorption takes place. The first step of the theoretical part was the optimisation of a dry surface model and then the investigation of water adsorption. The calculated molecular water adsorption energies are consistent with previously published experimental data and it appears that even though it is slightly less stable, the dissociative water sorption can also take place. This assumption was considered, in a second step, on a larger surface model where molecular and dissociated water molecules were adsorbed together with different ratio. It was found that, due to hydrogen bonding stabilisation, molecular and dissociated water molecules can coexist on the surface if the ratio of dissociated water molecules is less than ≈33%. These results are consistent with previous experimental works giving a 10–25% range

Uranium(VI) and europium(III) speciation at the phosphate compounds-solution interface

Prediction of radionuclides migration through a geosphere is of fundamental interest in order to evaluate the safety of an underground radwastes repository. We have studied uranyl and europium(III) ion sorption mechanisms onto three phosphate compounds: ZrP2O7; Zr2O(PO4)(2), and Th-4(PO4)(4)P2O7. A spectroscopic investigation which has been previously reported has allowed one to determine all species involved in the sorption processes under study. This paper presents the modeling of experimental retention data using FITEQLv3.2 code (constant capacitance model). All sorption isotherms were successfully simulated with respect to the structural constraints. We have shown that uranyl sorption onto the solids under study is less influenced by electrostatic interactions between aqueous species and charges. on the surface than is that for europium(III) ion. Because; many experimental constraints, obtained from independent spectroscopic techniques, have been taken into account for the fitting procedure, the sorption constant values can be determined accurately

Interaction Mechanisms between Uranium(VI) and Rutile Titanium Dioxide: From Single Crystal to Powder

This paper is devoted to the study of the mechanisms of interaction between uranyl ion and rutile TiO2. Among the radionuclides of interest, U(VI) can be considered as a model of the radionuclides oxo-cations. The substrate under study here is the rutile titanium dioxide (TiO2) which is an interesting candidate as a methodological solid since it can be easily found as powder and as manufactured single crystals. This material presents also a wide domain of stability as a function of pH. Then, it allows the study of the retention processes on well-defined crystallographic planes, which can lead to a better understanding of the surface reaction mechanisms. Moreover, it is well-established that the (110) crystallographic orientation is dominating the surface chemistry of the rutile powder. Therefore, the spectroscopic results obtained for the U(VI)/rutile (110) system and other relevant crystallographic orientations were used to have some insight on the nature of the uranium surface complexes formed on rutile powder. This goal was achieved by using time-resolved laser-induced fluorescence spectroscopy (TRLFS) which allows the investigation, at a molecular scale, of the nature of the reactive surface sites as well as the surface species. For rutile surfaces, oxygen atoms can be 3-fold, 2-fold (bridging oxygens), or single-fold (top oxygens) coordinated to titanium atoms. However, among these three types of surface oxygen atoms, the 3-fold coordinated ones are not reactive toward water molecules or aqueous metallic cations. This study led to conclude on the presence of two uranium(VI) surface complexes: the first one corresponds to the sorption of aquo UO22+ ion sorbed on two bridging oxygen atoms, while the second one, which is favored at higher surface coverages, corresponds to the retention of UO22+ by one bridging and one top oxygen atom. Thus, the approach presented in this paper allows the establishment of experimental constraints that have to be taken into account in the modeling of the sorption mechanisms

Speciation of uranium (VI) at the solid/solution interface: sorption modeling on zirconium silicate and zirconium oxide

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Molecular approach of the uranyl/mineral interfacial phenomena

Afin de comprendre, à l'échelle moléculaire, les mécanismes impliqués dans les interactions entre radionucléides et minéral, des études thermodynamiques et structurales sont présentées. Les argiles constituant une famille de substrats complexes, il est nécessaire de réaliser ce type d'étude sur des phases unitaires représentatives, afin d'extrapoler ensuite ces résultats aux solides naturels. Sont examinés, dans cette revue, les processus de sorption de l'uranium hexavalent sur la montmorillonite, TiO2 (poudre et monocristal) et également sur l'alumine et la silice. Les constantes de sorption correspondantes sont déterminées en utilisant les résultats structuraux obtenus à l'aide des techniques spectroscopiques suivantes : spectrofluorimétrie laser, spectroscopie de photoélectrons X, génération de seconde harmonique et spectroscopie d'absorption X. De plus, pour TiO2, ces résultats sont comparés à des calculs périodiques utilisant la théorie de la fonctionnelle de la densité, qui permettent d'accéder à la distribution des atomes à l'interface ainsi qu'à la stabilité relative des complexes de surface

Surface complexation modeling of uranium(VI) sorbed onto lanthanum monophosphate

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