Fast Chemical Contrast by X-ray Fluorescence Intensity Ratio Detection.

We describe a protocol for efficient detection of the chemical state of an element based on X-ray emission (fluorescence) spectroscopy using a Bragg optics spectrometer. The ratio of intensities at two appropriately chosen X-ray emission energies is a self-normalized quantity largely free of experimental artifacts and can thus be recorded with high accuracy. As the X-ray fluorescence lines are chemically sensitive, the intensity ratio identifies the chemical state. Differences between chemical states in spatially inhomogeneous or temporally evolving samples can be identified already with low numbers of photon events. This reduces the time required for data acquisition by 2 orders of magnitude as compared to recording a full spectrum.

Chemical Information in the L3 X-ray Absorption Spectra of Molybdenum Compounds by High-Energy-Resolution Detection and Density Functional Theory.

X-ray spectroscopy using high-energy-resolution fluorescence detection (HERFD) has critically increased the information content in X-ray spectra. We extend this technique to the tender X-ray range and present a study at the L3-edge of molybdenum. We show how information on the oxidation state, phase composition, and local environment in molybdenum-based compounds can be obtained by analyzing the HERFD L3 X-ray absorption near-edge structure (XANES). We demonstrate that the chemical shift of the L3-edge HERFD spectra follows a parabolic dependence on the oxidation state and show that a qualitative analysis of high-resolution spectra can help to estimate parameters such as distortion of a ligand environment and radial order of atoms around the absorber. In certain cases, the spectra allow disentangling the contributions from bond lengths and angles to the distortion of the ligand polyhedron. Comparison of the high-resolution spectra with theoretical simulations shows that the single-electron approximation is able to reproduce the spectral shape. The results of this work may be useful in every branch of physics, inorganic and organometallic chemistry, catalysis, materials science, biochemistry, and mineralogy where observed changes in performance or chemical properties of Mo-based compounds, accompanied by small changes in spectral shape, are to be related to the details of electronic structure and local atomic environment.

The five-analyzer point-to-point scanning crystal spectrometer at ESRF ID26.

X-ray emission spectroscopy in a point-to-point focusing geometry using instruments that employ more than one analyzer crystal poses challenges with respect to mechanical design and performance. This work discusses various options for positioning the components and provides the formulas for calculating their relative placement. Ray-tracing calculations were used to determine the geometrical contributions to the energy broadening including the source volume as given by the beam footprint on the sample. The alignment of the instrument is described and examples are given for the performance.

Temperature-Driven Self-Doping in Magnetite.

Magnetite is one of the most fascinating materials exhibiting the enigmatic first-order Verwey transition which is conventionally manipulated through chemical doping. Here, we show that heating magnetite results in a spontaneous charge reordering and, consequently, a hole self-doping effect at the octahedral sublattice. Core-level x-ray spectroscopy measurements combined with theory uncovers that there are three regimes of self-doping that map the temperature dependence of the electrical conductivity and magnetism up to the Curie temperature. Our results provide an elegant analogy between the effect of chemical doping and temperature-driven self-doping on trimerons in magnetite.

Demethylation of Methylmercury in Bird, Fish, and Earthworm.

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate [Hg(Sec)4] complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy (HR-XANES) and chromatography-inductively coupled plasma mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.

TEXS: in-vacuum tender X-ray emission spectrometer with 11 Johansson crystal analyzers.

The design and first results of a large-solid-angle X-ray emission spectrometer that is optimized for energies between 1.5 keV and 5.5 keV are presented. The spectrometer is based on an array of 11 cylindrically bent Johansson crystal analyzers arranged in a non-dispersive Rowland circle geometry. The smallest achievable energy bandwidth is smaller than the core hole lifetime broadening of the absorption edges in this energy range. Energy scanning is achieved using an innovative design, maintaining the Rowland circle conditions for all crystals with only four motor motions. The entire spectrometer is encased in a high-vacuum chamber that allocates a liquid helium cryostat and provides sufficient space for in situ cells and operando catalysis reactors.

X-ray Raman spectroscopy of lithium-ion battery electrolyte solutions in a flow cell.

The effects of varying LiPF6 salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium-ion battery electrolyte solvents (ethylene carbonate-dimethyl carbonate and propylene carbonate) have been investigated. X-ray Raman scattering spectroscopy (a non-resonant inelastic X-ray scattering method) was utilized together with a closed-circle flow cell. Carbon and oxygen K-edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li+ ion concentration in the solvent manifests itself as a blue-shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K-edge results agree with previous soft X-ray absorption studies on LiBF4 salt concentration in propylene carbonate, carbon K-edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.

Chemically resolved interface structure of epitaxial graphene on SiC(0001).

Atomic-layer 2D crystals have unique properties that can be significantly modified through interaction with an underlying support. For epitaxial graphene on SiC(0001), the interface strongly influences the electronic properties of the overlaying graphene. We demonstrate a novel combination of x-ray scattering and spectroscopy for studying the complexities of such a buried interface structure. This approach employs x-ray standing wave-excited photoelectron spectroscopy in conjunction with x-ray reflectivity to produce a highly resolved chemically sensitive atomic profile for the terminal substrate bilayers, interface, and graphene layers along the SiC[0001] direction.

Pt/CeO2 as Catalyst for Nonoxidative Coupling of Methane: Oxidative Regeneration.

Direct nonoxidative coupling is a promising route for methane upgrading, yet its commercialization is hindered by the lack of efficient catalysts. Pt/CeO2 catalysts with isolated Pt species have attracted an increasing amount of interest in recent years. Herein, we studied the catalytic role and evolution of isolated Pt centers on CeO2 prepared by flame spray pyrolysis under the harsh reaction conditions of nonoxidative methane coupling. During the reaction at 800 °C, the isolated Pt sites sinter, leading to a loss of the ethylene and ethane yield. The agglomerated Pt can be redispersed by using an in situ regeneration strategy in oxygen. We found that isolated Pt centers are able to activate methane only at the initial reaction stage, and the CePt5 alloy acts as the active phase in the prolonged reaction.

Flow cell for operando X-ray photon-in-photon-out studies on photo-electrochemical thin film devices.

Background: Photo-electro-chemical (PEC) water splitting represents a promising technology towards an artificial photosynthetic device but many fundamental electronic processes, which govern long-term stability and energetics, are not yet fully understood. X-ray absorption spectroscopy (XAS), and particularly its high energy resolution fluorescence-detected (HERFD) mode, emerges as a powerful tool to study photo-excited charge carrier behavior under operating conditions. The established thin film device architecture of PEC cells provides a well-defined measurement geometry, but it puts many constraints on conducting operando XAS experiments. It remains a challenge to establish a standardized thin film exchange procedure and concurrently record high-quality photoelectrochemical and X­ray absorption spectroscopy data that is unperturbed by bubble formation. Here we address and overcome these instrumental limitations for photoelectrochemical operando HERFD-XAS. Methods: We constructed a novel operando photo-electro-chemical cell by computer numerical control milling, guided by the materials' X­ray and visible light absorption properties to optimize signal detection. To test the cell's functionality, semiconducting thin film photoelectrodes have been fabricated via solution deposition and their photoelectrochemical responses under simulated solar light were studied using a commercial potentiostat in a three-electrode configuration during HERFD-XAS experiments at a synchrotron. Results: We demonstrate the cell's capabilities to measure and control potentiostatically and in open­circuit, to detect X­ray signals unperturbed by bubbles and to fluently exchange different thin film samples by collecting high-resolution Fe K-edge spectra of hematite ( α -Fe 2O 3) and ferrite thin film ( MFe 2O 4, M= Zn, Ni) photoelectrodes during water oxidation. Conclusions: Our cell establishes a measurement routine that will provide experimental access of photo-electro-chemical operando HERFD-XAS experiments to a broader scientific community, particularly due to the ease of sample exchange. We believe to enable a broad range of experiments which acquired fundamental insights will spur further photoelectrochemical research and commercialization of water splitting technologies.

X-ray studies bridge the molecular and macro length scales during the emergence of CoO assemblies.

The key to fabricating complex, hierarchical materials is the control of chemical reactions at various length scales. To this end, the classical model of nucleation and growth fails to provide sufficient information. Here, we illustrate how modern X-ray spectroscopic and scattering in situ studies bridge the molecular- and macro- length scales for assemblies of polyhedrally shaped CoO nanocrystals. Utilizing high energy-resolution fluorescence-detected X-ray absorption spectroscopy, we directly access the molecular level of the nanomaterial synthesis. We reveal that initially Co(acac)3 rapidly reduces to square-planar Co(acac)2 and coordinates to two solvent molecules. Combining atomic pair distribution functions and small-angle X-ray scattering we observe that, unlike a classical nucleation and growth mechanism, nuclei as small as 2 nm assemble into superstructures of 20 nm. The individual nanoparticles and assemblies continue growing at a similar pace. The final spherical assemblies are smaller than 100 nm, while the nanoparticles reach a size of 6 nm and adopt various polyhedral, edgy shapes. Our work thus provides a comprehensive perspective on the emergence of nano-assemblies in solution.

New reflections on hard X-ray photon-in/photon-out spectroscopy.

Analysis of the electronic structure and local coordination of an element is an important aspect in the study of the chemical and physical properties of materials. This is particularly relevant at the nanoscale where new phases of matter may emerge below a critical size. X-ray emission spectroscopy (XES) at synchrotron radiation sources and free electron lasers has enriched the field of X-ray spectroscopy. The spectroscopic techniques derived from the combination of X-ray absorption and emission spectroscopy (XAS-XES), such as resonant inelastic X-ray scattering (RIXS) and high energy resolution fluorescence detected (HERFD) XAS, are an ideal tool for the study of nanomaterials. New installations and beamline upgrades now often include wavelength dispersive instruments for the analysis of the emitted X-rays. With the growing use of XAS-XES, scientists are learning about the possibilities and pitfalls. We discuss some experimental aspects, assess the feasibility of measuring weak fluorescence lines in dilute, radiation sensitive samples, and present new experimental approaches for studying magnetic properties of colloidal nanoparticles directly in the liquid phase.

Insights into the Synthesis Mechanism of Ag29 Nanoclusters.

The current understanding of the synthesis mechanisms of noble metal clusters is limited, in particular for Ag clusters. Here, we present a detailed investigation into the synthesis process of atomically monodisperse Ag29 clusters, prepared via reduction of AgNO3 in the presence of dithiolate ligands. Using optical spectroscopy, mass spectrometry, and X-ray spectroscopy, it was determined that the synthesis involves a rapid nucleation and growth to species with up to a few hundred Ag atoms. From these larger species, Ag29 clusters are formed and their concentration increases steadily over time. Oxygen plays an important role in the etching of large particles to Ag29. No other stable Ag cluster species are observed at any point during the synthesis.

Characterization of High-k Nanolayers by Grazing Incidence X-ray Spectrometry.

The accurate characterization of nanolayered systems is an essential topic for today's developments in many fields of material research. Thin high-k layers and gate stacks are technologically required for the design of current and future electronic devices and can be deposited, e.g., by Atomic Layer Deposition (ALD). However, the metrological challenges to characterize such systems demand further development of analytical techniques. Reference-free Grazing Incidence X-ray Fluorescence (GIXRF) based on synchrotron radiation can significantly contribute to the characterization of such nanolayered systems. GIXRF takes advantage of the incident angle dependence of XRF, in particular below the substrate's critical angle where changes in the X-ray Standing Wave field (XSW) intensity influence the angular intensity profile. The reliable modeling of the XSW in conjunction with the radiometrically calibrated instrumentation at the PTB allows for reference-free, fundamental parameter-based quantitative analysis. This approach is very well suited for the characterization of nanoscaled materials, especially when no reference samples with sufficient quality are available. The capabilities of this method are demonstrated by means of two systems for transistor gate stacks, i.e., Al2O3 high-k layers grown on Si or Si/SiO2 and Sc2O3 layers on InGaAs/InP substrates.