Oxygen vacancy clusters in bulk cerium oxide and the impact of gold atoms

Ceria is important for catalysis due to its ability to form and utilize oxygen vacancies during redox reactions. Understanding the dynamic formation of the oxygen vacancies has contributed to the development of efficient catalytic processes. Here, we demonstrate the presence of oxygen vacancy clusters in the bulk of ceria and gold/ceria catalysts upon anaerobic carbon monoxide oxidation and describe their interplay with the orbital hybridization of Ce3+ 4f and 5d states. Observations are made using in situ X-ray Raman scattering spectroscopy at O K-and Ce N4,5-edges and in situ X-ray diffraction. These, combined with multiplet calculations, allow detection of the formation of Ce3+ in gold/ceria upon low temperature carbon monoxide oxidation. The modifications observed at the O K-edge reflect the rearrangement of the bulk oxygen sublattice. Density-functional theory calculations show vacancy ordering in the bulk, and explain modifications at the O K-edge, involving the hybridization of the Ce 4f and 5d and O 2p orbitals

Hydration in aqueous NaCl

Atomistic details about the hydration of ions in aqueous solutions are still debated due to the disordered and statistical nature of the hydration process. However, many processes from biology, physical chemistry to materials sciences rely on the complex interplay between solute and solvent. Oxygen K-edge X-ray excitation spectra provide a sensitive probe of the local atomic and electronic surrounding of the excited sites. We used ab initio molecular dynamics simulations together with extensive spectrum calculations to relate the features found in experimental oxygen K-edge spectra of a concentration series of aqueous NaCl with the induced structural changes upon solvation of the salt and distill the spectral fingerprints of the first hydration shells around the Na+- and Cl−-ions. By this combined experimental and theoretical approach, we find the strongest spectral changes to indeed result from the first hydration shells of both ions and relate the observed shift of spectral weight from the post- to the main-edge to the origin of the post-edge as a shape resonance. </p

Quantification of non-bridging oxygens in silicates using X-ray Raman scattering

International audienceDetecting and quantifying non-bridging oxygen (NBO) atoms is of particular interest for understanding the physical properties of melts or compressed materials, and requires an unequivocal spectral signature usable during in-situ measurements. In this paper, we evidence a low-energy feature of NBO in lithium silicate crystals using X-ray Raman scattering (XRS) spectroscopy around the energy losses of the oxygen K edge. A specific peak at 534-535 eV in the edge onset is unequivocally attributed to the presence of NBO. Its intensity is used to quantify NBO in lithium silicate glasses. A similar feature at low energy has also been evidenced in Na 2 SiO 3 and MgSiO 3 , generalizing the method to other alkali and alkali-earth silicates. This non-destructive method of NBO quantification, which is based on an X-ray inelastic scattering technique, can be extended to other spectroscopies such as electron-energy loss spectroscopy, soft x-ray absorption spectroscopy at the oxygen K edge

Correlation between mechanical and structural properties as a function of temperature within the TeO2–TiO2–ZnO ternary system

International audienceIn situ Raman spectroscopy, Resonance Frequency and Damping Analysis (RFDA) setup and Associated Raman Brillouin Calorimeter (ARABICA) setup experiments as a function of temperature were conducted on the (100-x)TeO2-5TiO2-xZnO (x=15; 17.5; 20; 22.5; 25) glass system. Structural and mechanical properties showed non-conventional properties evolution as a function of ZnO content which are managed by the modification of ZnO polyhedra. Before glass transition temperature (Tg), the evolution of the Boson peak (BP) frequencies and the elastic properties are in accordance with the idea of the relaxation of the strains inside the glass; after Tg, their evolution shows the transition toward a viscous liquid. BP and mechanical properties study evidences that as nano-heterogeneous domains size increases at a faster rate, the mechanical properties will decrease at a slower rate. This point will be helpful for choosing appropriate composition for optical fiber shaping

Hydration in aqueous NaCl

Atomistic details about the hydration of ions in aqueous solutions are still debated due to the disordered and statistical nature of the hydration process. However, many processes from biology, physical chemistry to materials sciences rely on the complex interplay between solute and solvent. Oxygen K-edge X-ray excitation spectra provide a sensitive probe of the local atomic and electronic surrounding of the excited sites. We used ab initio molecular dynamics simulations together with extensive spectrum calculations to relate the features found in experimental oxygen K-edge spectra of a concentration series of aqueous NaCl with the induced structural changes upon solvation of the salt and distill the spectral fingerprints of the first hydration shells around the Na+- and Cl--ions. By this combined experimental and theoretical approach, we find the strongest spectral changes to indeed result from the first hydration shells of both ions and relate the observed shift of spectral weight from the post- to the main-edge to the origin of the post-edge as a shape resonance

Joint Bone Spine

PURPOSE: Post-operative instrumented spine infection (PISI) is an infrequent complication. Diagnosis of spinal implant infection can be difficult, especially in case of chronic infection. METHODS: This retrospective study attempts to evaluate the diagnostic performance of [18F]fluorodeoxyglucose positron emission tomography/computed tomography (PET/CT) in PISI. Imagings were performed between April 2010 and June 2018 among patients referred for suspected chronic spinal implant infection. PET/CT were performed more than 12 weeks after surgery. PET/CT images were re-interpreted independently by two nuclear medicine physicians without knowledge of the patient's conditions. PET/CT data were analyzed both visually and semi-quantitatively (SUVmax). MRI results were collected from medical records. The final diagnosis of infection was based on bacteriological cultures or a twelve-month follow-up. RESULTS: Forty-nine PET/CT were performed in 44 patients (22 women, median age 65.0 years). Twenty-two patients had a diagnosis of infection during follow-up. Sensitivity, specificity, positive predictive value (PPV) and negative predictive value (NPV) for PET/CT were 86.4%, 81.5%, 79.2%, and 88.0%. Sensitivity, specificity, PPV and NPV were 66.7%, 75.0%, 66.0%, 75.0% respectively for MRI and 50.0%, 92.6%, 84.6% and 69.4% for serum C-reactive protein (CRP). Although these values were higher for PET/CT than for MRI or CRP, the differences were not statistically significant. In this setting, false positives with PET/CT can be observed in case of previous spine infection or adjacent segments disc disease. False negatives can result of extensive instrumented arthrodesis or infection with low virulence bacteria. CONCLUSION: PET/CT is useful for the diagnosis of PISI. These results should be evaluated in further prospective study