Structural and electronic transformations of GeSe glass under high pressures studied by X-ray absorption spectroscopy.

Pressure-induced transformations in an archetypal chalcogenide glass (GeSe) have been investigated up to 157 GPa by X-ray absorption spectroscopy (XAS) and molecular dynamics (MD) simulations. Ge and Se K-edge XAS data allowed simultaneous tracking of the correlated local structural and electronic changes at both Ge and Se sites. Thanks to the simultaneous analysis of extended X-ray absorption fine structure (EXAFS) signals of both edges, reliable quantitative information about the evolution of the first neighbor Ge-Se distribution could be obtained.

A novel electrochemical flow-cell for XAS investigations in X-ray opaque supports.

Improvement of electrochemical technologies is one of the most popular topics in the field of renewable energy. However, this process requires a deep understanding of the electrode-electrolyte interface behavior under conditions. X-ray absorption spectroscopy (XAS) is widely employed to characterize electrode materials, providing element-selective oxidation state and local structure.

Oxide Coating Role on the Bulk Structural Stability of Active LiMnO Cathodes.

The protective coating of the electrode materials is a known source of improvement of the cycling performances in battery devices. In the case of the LiMnO cathodes, the coating with a thin alumina layer has been proven to show performance efficiency. However, the precise mechanism of its effect on the performance improvement of the electrodes is still not clear.

EXAFS investigations on the pressure induced local structural changes of GeSeglass under different hydrostatic conditions.

Pressure-induced transformations in glassy GeSehave been studied using the x-ray absorption spectroscopy. Experiments have been carried out at the scanning-energy beamline BM23 (European Synchrotron Radiation Facility) providing a micrometric x-ray focal spot up to pressures of about 45 GPa in a diamond anvil cell. Both Se and Ge K-edge experiments were performed under different hydrostatic conditions identifying the metallization onsets by accurate determinations of the edge shifts.

Advances in modelling X-ray absorption spectroscopy data using reverse Monte Carlo.

Modern extended X-ray absorption fine structure (EXAFS) analysis is based on multiple-scattering calculations. Those calculations are carried out for fixed atomic configurations and proper account of the thermal and static disorder, corresponding to well-defined pair and higher-order distribution functions, can be obtained using different methods. The application of the Reverse Monte Carlo (RMC) method is able to provide tridimensional models of the atomic structure compatible with a given set of experimental data, producing useful and consistent structural models.

Emerging oxidized and defective phases in low-dimensional CrCl.

Two-dimensional (2D) magnets such as chromium trihalides CrX (X = I, Br, Cl) represent a frontier for spintronics applications and, in particular, CrCl has attracted research interest due its relative stability under ambient conditions without rapid degradation, as opposed to CrI. Herein, mechanically exfoliated CrCl flakes are characterized at the atomic scale and the electronic structures of pristine, oxidized, and defective monolayer CrCl phases are investigated employing density functional theory (DFT) calculations, scanning tunneling spectroscopy (STS), core level X-ray photoemission spectroscopy (XPS), and valence band XPS and ultraviolet photoemission spectroscopy (UPS). As revealed by atomically resolved transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis, the CrCl flakes show spontaneous surface oxidation upon air exposure with an extrinsic long-range ordered oxidized O-CrCl structure and amorphous chromium oxide formation on the edges of the flakes.

A new internally heated diamond anvil cell system for time-resolved optical and x-ray measurements.

We have developed a new internally heated diamond anvil cell (DAC) system for in situ high-pressure and high-temperature x-ray and optical experiments. We have adopted a self-heating W/Re gasket design allowing for both sample confinement and heating. This solution has been seldom used in the past but proved to be very efficient to reduce the size of the heating spot near the sample region, improving heating and cooling rates as compared to other resistive heating strategies.

Band Gap Implications on Nano-TiO₂ Surface Modification with Ascorbic Acid for Visible Light-Active Polypropylene Coated Photocatalyst.

The effect of surface modification using ascorbic acid as a surface modifier of nano-TiO₂ heterogeneous photocatalyst was studied. The preparation of supported photocatalyst was made by a specific paste containing ascorbic acid modified TiO₂ nanoparticles used to cover Polypropylene as a support material. The obtained heterogeneous photocatalyst was thoroughly characterized (scanning electron microscope (SEM), RAMAN, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Diffuse Reflectance Spectra (DRS) and successfully applied in the visible light photodegradation of Alizarin Red S in water solutions.

Structure of Water in Zn Aqueous Solutions from Ambient Conditions up to the Gigapascal Pressure Range: A XANES and Molecular Dynamics Study.

The structural modifications induced on a 0.5 M Zn aqueous solution by increasing the pressure to 6.4 GPa were investigated using a combination of X-ray absorption near edge structure (XANES) spectroscopy and molecular dynamics (MD) simulations.

Is the Solid Electrolyte Interphase an Extra-Charge Reservoir in Li-Ion Batteries?

Advanced metal oxide electrodes in Li-ion batteries usually show reversible capacities exceeding the theoretically expected ones. Despite many studies and tentative interpretations, the origin of this extra-capacity is not assessed yet. Lithium storage can be increased through different chemical processes developing in the electrodes during charging cycles.

EIS: the scattering beamline at FERMI.

The Elastic and Inelastic Scattering (EIS) beamline at the free-electron laser FERMI is presented. It consists of two separate end-stations: EIS-TIMEX, dedicated to ultrafast time-resolved studies of matter under extreme and metastable conditions, and EIS-TIMER, dedicated to time-resolved spectroscopy of mesoscopic dynamics in condensed matter. The scientific objectives are discussed and the instrument layout illustrated, together with the results from first exemplifying experiments.

Hydration properties of the Zn2+ ion in water at high pressure.

The structure and dynamics of water in ionic solutions at high pressure have been investigated using a combined approach based on extended X-ray absorption fine structure (EXAFS) spectroscopy and Molecular Dynamics (MD) simulations. Modification of the hydration properties of the Zn(2+) ion induced by a pressure increase from ambient condition up to ∼6.4 GPa has been revealed and accurately analyzed.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles.

Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure.

We report the nearest-neighbor oxygen-oxygen radial distribution function (NN O-O RDF) of room temperature liquid water and polycrystalline ice Ih (-16.8 degrees C) obtained by x-ray Raman based extended x-ray absorption fine structure (EXAFS) spectroscopy. The spectra of the two systems were taken under identical experimental conditions using the same procedures to obtain the NN O-O RDFs.

Performance of a fuel cell optimized for in situX-ray absorption experiments.

A commercial fuel cell has been successfully modified to carry out X-ray absorption spectroscopy (XAS) measurements under optimized in operando conditions. The design is conceived for the performance of XAS experiments in transmission mode over a wide range of X-ray energies above 6 keV, owing to the reduced absorption of the cell. The wide angular aperture allows the collection of XAS in fluorescence mode and of X-ray diffraction patterns when needed.

Is there icosahedral ordering in liquid and undercooled metals?

The local structure of simple liquids is significantly different from that of corresponding crystalline systems. Signatures of fivefold local ordering have been previously found, but current knowledge is limited to pair distribution, leaving considerable uncertainty in the determination of the geometrical structure. New x-ray absorption experimental results on liquid and undercooled liquid copper, interpreted using an advanced data-analysis method based on multiple-scattering simulations, are shown to contain direct information on triplet correlations making feasible a reliable determination of the bond-angle distribution and fraction of nearly icosahedral configurations in liquids.

Local structure in molecular complexes probed by multiple-scattering XAS.

The GNXAS (n-body distribution function X-ray absorption spectroscopy) method for multiple-scattering (MS) data analysis of EXAFS (extended X-ray absorption fine structure) data and the results recently obtained on molecular complexes relevant to biological matter are briefly reviewed and discussed. Practical MS calculations for important molecular fragments like Fe-O-O and Fe-C-N-Cu are presented in detail showing the potential of the techniques for measuring bond-angle distributions. The optimal conditions for obtaining accurate structural refinements using EXAFS measurements and modern data-analysis schemes are discussed as well as the current perspectives in the exploitation of the technique.

Multiple-Edge XAS Studies of Synthetic Iron-Copper Bridged Molecular Assemblies Relevant to Cytochrome c Oxidase. Structure Determination Using Multiple-Scattering Analysis with Statistical Evaluation of Errors.

An X-ray absorption spectroscopy study has been carried out at the Fe and Cu K-edges for two bridged molecular assemblies, both of which contain an Fe-X-Cu (X = O(2)(-), OH(-)) bridge unit, some of whose features are relevant to the binuclear site of cytochrome c oxidase. The two complexes [(OEP)Fe-O-Cu(Me(6)tren)](1+) and [(OEP)Fe-(OH)-Cu(Me(5)tren)(OClO(3))](1+) have similar structural fragments around the metal centers except that they differ significantly in the bridge structure (the former contains a linear oxo bridge while the latter has a bent hydroxo bridge). We report a comparative study of these complexes using multiple-scattering (MS) EXAFS analysis and the program package GNXAS.