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NbAs is a Weyl semimetal and belongs to the group of topological phases that exhibit distinct quantum and topological attributes. Topological phases have a fundamentally different response to external perturbations, such as magnetic fields. To obtain insights into the response of such phases to pressure, we conducted a comprehensive study on the pressure-induced electronic and structural transitions in NbAs. We used micro-X-ray diffraction (XRD) and micro-X-ray spectroscopy (XAS) techniques to elucidate the changes at different atomic and electronic length scales (local, medium, and bulk) as combined with theoretical calculations. High-pressure XRD measurements revealed a rather common compression behavior up to ~12 GPa that could be fitted to an equation of state formalism with a bulk modulus of K 0 = 179.6 GPa. Complementary Nb K-edge XAS data unveiled anomalies at pressure intervals of ~12–15 and ~25–26 GPa in agreement with previous literature data from XRD studies. We attribute these anomalies to a previously reported topological Lifshitz transition and the tetragonal-to-hexagonal phase transition, respectively. Analysis of EXAFS results revealed slight changes in the mean next-nearest neighbor distance Nb–As(1) (~2.6 Å) at ~15 GPa, while the second nearest neighboring bond Nb–Nb(1) (~3.4 Å) shows a pronounced anomaly. This indicates that the electronic changes across the Lifshitz transition are accommodated first in the medium-range atomic structure and then at the local range and bulk. The variances of these bonds show anomalous but progressive evolutions close to the tetragonal-to-hexagonal transition at ~25 GPa, which allowed us to derive the evolution of vibration properties in this material. We suggest a prominent displacive character of the I 4 1 m d → P 6 ¯ m 2 transition facilitated by phonon modes. [ABSTRACT FROM AUTHOR]

Two-dimensional borophene nanosheets are sensitive to oxygen, which has hindered their development and use in scientific research and subsequent applications. Conventional methods of borophene synthesis are based on its epitaxial growth on single-crystal metal substrates by using molecular beam epitaxy (MBE). The electron deficiency of boron atoms in the borophene structure has made the use of metal substrates in the growth process inevitable. Hence, a method to stabilize the borophene sheets for further applications seems necessary. In this work, the oxidation arrangement of Al-activated chemical vapor deposition (CVD) of borophene sheets was investigated via scanning photoemission microscopy (SPEM). This method allows the investigation of oxidation ordering via its high spatial resolution and elemental sensitivity. The results indicate the persistence of the borophene χ3 (and some β12) phase after exposure to air. The formation of boron oxide is primarily limited to the Al aggregated islands and the edges while maintaining the borophene configuration intact. Our results show that the electronic exchange between the Al aggregates and the interface of boron atoms at the edges of the borophene sheet can prevent the oxidation process and preserve the borophene sheets for long periods. The lower oxidation tendency of the Al-saturated borophene was confirmed via density functional theory calculation, showing a lower oxygen binding energy on Al/borophene compared with that of the metal-free borophene. The oxidation-resistive borophene can be exploited in innovative high-efficiency catalytic, electronic, and sensing devices. [ABSTRACT FROM AUTHOR]

Pressure-induced transformations in an archetypal chalcogenide glass (GeSe2) 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. It also allowed to account for contributions of the Ge-Ge and Se-Se bond distributions (chemical disorder). The low-density to high-density amorphous-amorphous transformation was found to occur within 10 to 30 GPa pressure range, but the conversion from tetrahedral to octahedral coordination of the Ge sites is completed above ~ 80 GPa. No convincing evidence of another high-density amorphous state with coordination number larger than six was found within the investigated pressure range. The number of short Ge-Ge and Se-Se "wrong" bonds was found to increase upon pressurization. Experimental XAS results are confirmed by MD simulations, indicating the increase of chemical disorder under high pressure. [ABSTRACT FROM AUTHOR]

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 operando conditions. X-ray absorption spectroscopy (XAS) is widely employed to characterize electrode materials, providing element-selective oxidation state and local structure. Several existing cells allow studies as close as possible to realistic operating conditions, but most of them rely on the deposition of the electrodes on conductive and X-ray transparent materials, from where the radiation impinges the sample. In this work, we present a new electrochemical flow-cell for operando XAS that can be used with X-ray opaque substrates, since the signal is effectively detected from the electrode surface, as the radiation passes through a thin layer of electrolyte (∼17 μm). The electrolyte can flow over the electrode, reducing bubble formation and avoiding strong reactant concentration gradients. We show that high-quality data can be obtained under operando conditions, thanks to the high efficiency of the cell from the hard X-ray regime down to ∼4 keV. We report as a case study the operando XAS investigation at the Fe and Ni K-edges on Ni-doped γ-Fe2O3 films, epitaxially grown on Pt substrates. The effect of the Ni content on the catalytic performances for the oxygen evolution reaction is discussed. [ABSTRACT FROM AUTHOR]

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. This method has been proposed and applied also to EXAFS data by several authors in the last 25 years and has been fully implemented in the framework of the RMC-GnXAS method for EXAFS data-analysis. Here we present the extension and application of this method to multiple-edge studies of molecules, crystalline solids and liquids, including the long-range constraints provided by other techniques (e.g. diffraction). The potential and possible weaknesses of the RMC method are discussed, as well as the importance of accounting for the effect of noise levels in XAFS data. Results of RMC refinements are reported for several exemplary cases including Br2 and GeI4 molecular gases, crystalline Ge and AgBr, amorphous Ge and liquid AgBr. Those applications show the general interest for this method, and the importance of combining multiple set of data for improving the accuracy of the structural refinement both at short and long range. [ABSTRACT FROM AUTHOR]

The structure of the Ga85.8In14.2 eutectic liquid alloy is investigated both under ambient conditions and at high pressure/high temperature using X‐ray absorption spectroscopy (XAS) and X‐ray diffraction (XRD) techniques. The local structure of the liquid alloy at ambient conditions is analyzed using double‐edge refinements of the XAS data. Solid–liquid phase transitions under high‐pressure and high‐temperature conditions are monitored by combined XAS and XRD measurements along several quasi‐isobaric heating runs, allowing to draw a melting line up to 10 GPa. The established melting line is found to be slightly below the one of pure gallium (Ga) and to follow its trend as expected from the eutectic nature of the compound. A series of Ga K‐edge X‐ray absorption fine structure (XAFS) spectra measured at different pressures indicates the absence of large structural modifications at local Ga sites in the liquid within the investigated pressure and temperature range. [ABSTRACT FROM AUTHOR]

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. The system has been widely tested under high-temperature conditions by performing several thermal emission measurements. A robust relationship between electric power and average sample temperature inside the DAC has been established up to about 1500 K by a measurement campaign on different simple substances. A micro-Raman spectrometer was used for various in situ optical measurements and allowed us to map the temperature distribution of the sample. The distribution resulted to be uniform within the typical uncertainty of these measurements (5% at 1000 K). The high-temperature performances of the DAC were also verified in a series of XAS (x-ray absorption spectroscopy) experiments using both nano-polycrystalline and single-crystal diamond anvils. XAS measurements of germanium at 3.5 GPa were obtained in the 300 K–1300 K range, studying the melting transition and nucleation to the crystal phase. The achievable heating and cooling rates of the DAC were studied exploiting a XAS dispersive setup, collecting series of near-edge XAS spectra with sub-second time resolution. An original XAS-based dynamical temperature calibration procedure was developed and used to monitor the sample and diamond temperatures during the application of constant power cycles, indicating that heating and cooling rates in the 100 K/s range can be easily achieved using this device. [ABSTRACT FROM AUTHOR]

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 °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. This protocol ensured a measurement of the relative distance distribution with very small systematic errors. The NN O–O RDF of water is found to be more asymmetric (tail extending to longer distances) with longer average distance (2.81 Å for water and 2.76 Å for ice) but a slightly shorter peak position (2.70 Å for water and 2.71 Å for ice). The refinement also showed a small but significant contribution from the linear O–H–O multiple scattering signal. The high sensitivity to short range distances of the EXAFS probe will set further restrictions to the range of possible models of liquid water. [ABSTRACT FROM AUTHOR]

The many advantages of Na-ion batteries (NIBs) in terms of availability and cost of raw materials compared with Li-ion batteries (LIBs) are hindered by the stability of Na-based electrodes. The most promising NIB positive electrodes are Co- and Ni-free sodium manganese rich layered oxides with the general formula UGRAPHIC DISPLAY="INLINE" ID="UGT1" SRC="UGT1"/ (y ＜ 0.33, TM = transition metal/s). Although their stability is greatly improved when doped with electrochemically inactive species such as Mg or Ti, the rationale behind this has not been understood to date. Here, we demonstrate how a given degree of TiIV doping (z = 0.1) helps to stabilize the crystal structure of sodium manganese rich layered oxides by absorbing electrochemically induced strain; a remarkable step forward on the quest of finding the best NIB positive electrode. In this case, any Mn–Ti substitution below z = 0.1 will not be enough to absorb the strain and substitutions above this value will increase the amount of Jahn–Teller active MnIII leading to destabilization of the crystal structure with poor electrochemical performance. The possibility of controlling structural and electrochemical properties by TM substitution is the starting point towards the design of electrode materials that will ultimately lead towards competitive Na-ion batteries. [ABSTRACT FROM AUTHOR]

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. In particular, this new supported TiO2 photocatalyst showed a change in the adsorption mechanism of dye with respect to that of only TiO2 due to the surface properties. In addition, an improvement of photocatalytic performances in the visible light photodegration was obtained, showing a strict correlation between efficiency and energy band gap values, evidencing the favorable surface modification of TiO2 nanoparticles. [ABSTRACT FROM AUTHOR]

We present a combined experimental and theoretical Pb‐L3 X‐ray absorption near‐edge spectroscopy (XANES) to investigate the chemical state of Pb in transition metal perovskites PbTMO3 (TM = Ti, Ni). A pre‐edge feature originated from the excitation of a 2p core electron to the 6s orbital is only observed in PbNiO3, from which the valence of Pb is determined to be Pb4+ with two 6s holes. However, no such 2p–6s related excitation was observed in PbTiO3, indicating the formation of Pb2+ with fully occupied 6s2 state in this materials. Our results demonstrate that this pre‐edge peak from dipole allowed 2p–6s transition is a sensitive finger‐print of the Pb valence state in solid state materials. [ABSTRACT FROM AUTHOR]

Currently available X-ray and extreme ultraviolet free electron laser (FEL) sources provide intense ultrashort photon pulses. Those sources open new exciting perspectives for experimental studies of ultrafast non-equilibrium processes at the nanoscale in condensed matter. Theoretical approaches and computer simulations are being developed to understand the complicated dynamical processes associated with the interaction of FEL pulses with matter. In this work, we present the results of the application of a simplified three-channel model to the non-equilibrium dynamics of ultrathin aluminum films excited by FEL radiation at 33.3, 37 and 92 eV photon energy. The model includes semi-classical rate equations coupled with the equation of propagation of the photon wave packets. X-ray transmission measurements are found to be in agreement with present simulations, which are also able to shed light on temporal dynamics (in the fs range) in nano-sized Al films strongly interacting with the photon pulse. We also expanded our non-linear model, explicitly including the two-photon absorption cross-section and the effect of including electron heating for reproducing transmission measurements. [ABSTRACT FROM AUTHOR]

The Reverse Monte Carlo (RMC) algorithm for structure refinement has been applied to x-ray absorption spectroscopy (XAS) multiple-edge data sets for six gas phase molecular systems (SnI2, CdI2, BBr3, GaI3, GeBr4, GeI4). Sets of thousands of molecular replicas were involved in the refinement process, driven by the XAS data and constrained by available electron diffraction results. The equilibrated configurations were analysed to determine the average tridimensional structure and obtain reliable bond and bond-angle distributions. Detectable deviations from Gaussian models were found in some cases. This work shows that a RMC refinement of XAS data is able to provide geometrical models for molecular structures compatible with present experimental evidence. The validation of this approach on simple molecular systems is particularly important in view of its possible simple extension to more complex and extended systems including metal-organic complexes, biomolecules, or nanocrystalline systems. [ABSTRACT FROM AUTHOR]

The evolution of the solid electrolyte interface (SEI) in carbon‐coated ZnFe2O4 (ZFO‐C) anodes is studied by soft X‐ray absorption spectroscopy (XAS). Experiments probe locally the SEI growth in the 2–100 nm range, using both total electron (TEY) and total fluorescence (TFY) yield techniques. XAS analysis shows that the SEI grows preferentially around the ZFO‐C nanoparticles. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. Due to the high Pt dilution, in situmeasurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situfluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situmeasurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5–2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports. [ABSTRACT FROM AUTHOR]

We describe a modular detector system suitable to intercept the diffracted x-ray radiation (Debye–Scherrer rings) in a transmission geometry setup at monochromatic tunable synchrotron radiation beamlines. The detector consists of several independent channels composed of a motorized front slit and a rear detector slit system which can be mounted in either a vertical or a horizontal configuration. The detectors are placed at fixed scattering angles 2θ and the diffraction scan is performed by tuning the monochromator energy. The availability of a multidetector system allows one to cover a wide range of scattering vectors with limited range energy scans. The photon sensitive elements are based on CdZnTe solid state detectors which are used at ambient temperature for high efficiency photon counting in the 10–60 keV range. In alternative, conventional NaI(Tl) scintillation detectors can be integrated in the setup. The system can be mounted in a high-resolution configuration and typical widths in the range ΔE/E=10[sup -3] have been obtained for Bragg peaks. In these conditions the sensitivity to changes in the lattice spacing is better than 10[sup -4]. This detector system fully complements the experimental devices usually available at x-ray absorption spectroscopy beamlines and the short range structural information obtained using the x-ray absorption fine structure technique. Typical applications include high-pressure and high-temperature investigations of condensed matter. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Modern XAFS (X-ray Absorption Fine Structure) data-analysis is based on accurate multiple-scattering (MS) calculations of the X-ray absorption cross-section. In this paper, we present the inclusion and test of relativistic corrections for the multiple-scattering calculations within the GnXAS suite of programs, which is relevant to the treatment of the XAFS signals when atoms with high atomic number are contained into the system. We present a suitable strategy for introducing relativistic corrections without altering the basic structure of the programs. In particular, this is realized by modifying only the Phagen program calculating the atomic absorption cross sections and scattering t-matrices for the selected cluster. The modification incorporates a pseudo-Schrödinger Equation (SE) replacing the Dirac relativistic form. The phase-shift calculations have been put to a test in two known molecular and crystalline cases: molecular bromine Br 2 and crystalline Pb. Calculations in an extended energy range have been shown to be very close to the non-relativistic case for Br 2 (Br K-edge) while corrections have been found to exceed 25% for amplitude and phases of the XAFS multiple-scattering signals (Pb L 3 -edge). Benefits in the structural refinement using relativistic corrections are discussed for crystalline Pb at room temperature. [ABSTRACT FROM AUTHOR]

Polymorphism of substances under high pressures is observed and used to obtain materials with new physical properties. Here the authors present experimental results revealing phase transitions and structure of liquid tin at high pressure under metastable conditions using x-ray absorption spectroscopy and x-ray diffraction. They show that there is an abrupt change in the undercooling limit of liquid Sn above 2 GPa, where nucleation takes place into the Sn-III metastable solid phase. The liquid local structure is found to be composed of tetrahedral and close-packed configurations. The latter are found to dominate at high pressure favoring crystallization to the Sn-III metastable solid phase. [ABSTRACT FROM AUTHOR]

In this study, a green and facile thermal reduction of graphene oxide using an eco-friendly system of d-(+)-glucose and NH4OH for the preparation of reduced graphene oxide was described. The obtained reduced graphene oxide dispersion was characterized by SEM, Dynamic Light Scattering, Raman and X-Ray Photoelectron Spectroscopy. TiO2 nanoparticles and reduced graphene oxide nanocomposites were successively prepared and used in the preparation of heterogeneous photocatalysts that were characterized by Atomic Force Microscopy and Photoluminescence Spectroscopy and subsequently tested as visible light photocatalysts for the photodegradation of Alizarin Red S in water as target pollutant. Obtained results of photocatalytic tests regarding the visible light photocatalytic degradation of Alizarin Red S demonstrated that the use of reduced graphene oxide in combination with TiO2 led to a significant improvement for both adsorption of Alizarin Red S on the catalyst surface and photodegradation efficiencies when compared to those obtained with not doped TiO2. [ABSTRACT FROM AUTHOR]

We describe state-of-the-art experimental techniques using the beamline BM29 of the European Synchrotron Radiation Facility (ESRF). This station exploits the unique characteristics of an ESRF bending magnet source to provide a tunable, collimated, x-ray beam to perform high quality x-ray absorption spectroscopy within the energy range of E=5-75 keV using Si(111), Si(311), and Si(511) crystal pairs. Energy scans can be performed over this wide energy range with excellent reproducibility, stability and resolution, usually better than ΔE/E=5x10[sup -5]. The experimental setup has been exploited to study condensed matter under extreme conditions. We describe here two sample environment devices; the L' Aquila-Camerino oven for high-temperature studies up to 3000 K in high vacuum and the Paris-Edinburgh press suitable for high-pressure high-temperature studies in the range 0.1-7 GPa and temperatures up to 1500 K. These devices can be integrated in an experimental setup which combines various control and detection systems suitable to perform x-ray absorption spectroscopy, x-ray absorption temperature scans, and energy scanning x-ray diffraction (ESXD). The ESXD setup is based on a scintillator detector behind a fixed angle collimator aligned to the sample. The combination of these three measurements, which can be performed in rapid sequence on the sample during the experiment, provides an essential tool for structural investigations and in situ sample characterization. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]