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The grazing emission X-ray fluorescence (GEXRF) technique offers a promising approach to determining the spatial distribution of various chemical elements in nanostructures. In this paper, we present a comparison with grazing incidence small-angle X-ray scattering (GISAXS), an established method for dimensional nanometrology, on periodic TiO

We used reference-free grazing incidence X-ray fluorescence to measure the density of four thiol Raman-active molecules assembled on gold surfaces. This value is needed to reliably quantify the number of molecules contributing to the SERS signal in a plasmonic substrate in the effort to standardize the enhancement factor calculation and such molecules constitute suitable probes for benchmarking SERS sensors.

International audience; In the present issue of Physica Status Solidi A readers will find a selection of 6 articles presented by participants during the 2021 E-MRS Spring Meeting Symposium M: ALTECH 2021 – Analytical techniques for precise characterization of nano materials. The Symposium M, organised by four major European National Metrology Institutes, covered current topics from the field of metrology for nanoscaled materials and aimed at stimulating discussion between scientists and engineers from metrology and research institutes, academia and industry.

Performing an x-ray scattering analysis can underpin the quantitative description of a sample of interest, for example, to complement an x-ray fluorescence analysis. However, the reliability of such an analytical approach depends on good knowledge of scattering coefficients (or scattering cross-sections), which describe the probability of interaction and are characteristic of each chemical element. In this work, a metrological study of experimentally determining differential Rayleigh and Compton scattering coefficients for nickel is presented. Angular scans of the scattering intensities at different positions are enabled by a flexible experimental set-up and, therefore, allow for the robust determination of differential scattering coefficients at a wide range of forward and backward scattering angles. As a result, scattering coefficients in the range from 0.117 ( 14 ) × 10 − 3 cm2 g−1 sr−1 to 33.7 ( 39 ) × 10 − 3 cm2 g−1 sr−1 were determined in the momentum transfer range of 12.1 nm−1 to 22.4 nm−1. In addition, utilizing monochromatized and highly linearly polarized synchrotron radiation ( E 0 = 30 keV ) ensures direct comparability to theoretical databases.

Self-assembled monolayers of 7-mercapto 4-methylcoumarin (MMC) on a flat gold surface were studied by Molecular Dynamics (MD) simulations, reference-free grazing incidence X-ray fluorescence (GIXRF) and X-ray photoemission spectroscopy (XPS), to determine the maximum monolayer density and to investigate the nature of the molecule/surface interface. In particular, the protonation state of the sulfur atom upon adsorption was analyzed, since some recent literature presented evidences for physisorbed thiols (preserving the S-H bond), unlike the common picture of chemisorbed thiyls (losing the hydrogen). MD with a specifically tailored force field was used to simulate either thiol or thiyl monolayers with increasing number of molecules, to determine the maximum dynamically stable densities. This result was refined by computing the monolayer chemical potential as a function of the density with the Bennet Acceptance Ratio method, based again on MD simulations. The monolayer density was measured with GIXRF, which provided a quantitative estimate of the number of sulfur atoms on top of flat gold surfaces embedded in a solution of MMC, to allow the formation of a dense monolayer. The sulfur core level binding energies in the same monolayers were measured by XPS, fitting the recorded spectra with the binding energies proposed in the literature for free or adsorbed thiols and thiyls, to get insight on the nature of the molecular species present in the layer.

Self-assembled monolayers (SAM) of 7-mercapto-4-methylcoumarin (MMC) on a flat gold surface were studied by molecular dynamics (MD) simulations, reference-free grazing incidence X-ray fluorescence (GIXRF) and X-ray photoelectron spectroscopy (XPS), to determine the maximum monolayer density and to investigate the nature of the molecule/surface interface. In particular, the protonation state of the sulfur atom upon adsorption was analyzed, since some recent literature presented evidence for physisorbed thiols (preserving the S-H bond), unlike the common picture of chemisorbed thiyls (losing the hydrogen). MD with a specifically tailored force field was used to simulate either thiol or thiyl monolayers with increasing number of molecules, to determine the maximum dynamically stable densities. This result was refined by computing the monolayer chemical potential as a function of the density with the bennet acceptance ratio method, based again on MD simulations. The monolayer density was also measured with GIXRF, which provided the absolute quantification of the number of sulfur atoms in a dense self-assembled monolayer (SAM) on flat gold surfaces. The sulfur core level binding energies in the same monolayers were measured by XPS, fitting the recorded spectra with the binding energies proposed in the literature for free or adsorbed thiols and thiyls, to get insight on the nature of the molecular species present in the layer. The comparison of theoretical and experimental SAM densities, and the XPS analysis strongly support the picture of a monolayer formed by chemisorbed, dissociated thiyls.

A reliable and quantitative material analysis is crucial for assessing new technological processes, especially to facilitate a quantitative understanding of advanced material properties at the nanoscale. To this end, X‐ray fluorescence microscopy techniques can offer an element‐sensitive and non‐destructive tool for the investigation of a wide range of nanotechnological materials. Since X‐ray radiation provides information depths of up to the microscale, even stratified or buried arrangements are easily accessible without invasive sample preparation. However, in terms of the quantification capabilities, these approaches are usually restricted to a qualitative or semi‐quantitative analysis at the nanoscale. Relying on comparable reference nanomaterials is often not straightforward or impossible because the development of innovative nanomaterials has proven to be more fast‐paced than any development process for appropriate reference materials. The present work corroborates that a traceable quantification of individual nanoobjects can be realized by means of an X‐ray fluorescence microscope when utilizing rather conventional but well‐calibrated instrumentation instead of reference materials. As a proof of concept, the total number of atoms forming a germanium nanoobject is quantified using soft X‐ray radiation. Furthermore, complementary dimensional parameters of such objects are reconstructed.

For the reliable fabrication of the current and next generation of nanostructures it is essential to be able to determine their material composition and dimensional parameters. Using the grazing incidence X-ray fluoresence technique, which is taking advantage of the X-ray standing wave field effect, nanostructures can be investigated with a high sensitivity with respect to the structural and elemental composition. This is demonstrated using lamellar gratings made of Si$_3$N$_4$. Rigorous field simulations obtained from a Maxwell solver based on the finite element method allow to determine the spatial distribution of elemental species and the geometrical shape with sub-nm resolution. The increasing complexity of nanostructures and demanded sensitivity for small changes quickly turn the curse of dimensionality for numerical simulation into a problem which can no longer be solved rationally even with massive parallelisation. New optimization schemes, e.g. machine learning, are required to satisfy the metrological requirements. We present reconstruction results obtained with a Bayesian optimization approach to reduce the computational effort., Event: SPIE Optical Metrology, 2019, Munich, Germany. arXiv admin note: text overlap with arXiv:1801.04157

The characterization of nanostructures and nanostructured surfaces with high sensitivity in the sub-nm range has gained enormously in importance for the development of the next generation of integrated electronic circuits. A reliable and non-destructive characterization of the material composition and dimensional parameters of nanostructures, including their uncertainties, is strongly required. Here, an optical technique based on grazing incidence X-ray fluorescence measurements is proposed. The reconstruction of a lamellar nanoscale grating made of Si3N4 is presented as an example. This technique uses the X-ray standing wave field, which arises due to interference between the incident and the reflected radiation, as nanoscale gauge. This enables the spatial distribution of the specific elements to be reconstructed using a finite-element method for the calculation of the standing wave field inside the material. For this, the optical constants for the constituent materials of the structure are needed. We derived them from soft X-ray reflectivity measurements on an unstructured part of the wafer sample. To counteract the expensive computation of the finite-element-Maxwell-solver, a Bayesian optimizer is exploited to obtain a most efficient sampling of the searched parameter space. The method is also used to determine the uncertainties of the reconstructed parameters. The homogeneity of the sample was also analyzed by evaluating several measurement spots across the grating area. For the validation of the reconstruction results, the grating line shape was measured by means of Atomic Force Microscopy.

Each battery suffers from degradation effects which lead to capacity fading and life cycle reduction. With electrochemical methods, the battery capacity decrease can easily be monitored, but they are inappropriate to comprehend the underlying chemical and physical properties responsible for the capacity fading. In the present paper, we demonstrate the power of X-ray spectrometry techniques to investigate the transition metal dissolution (TMD) fading process for manganese in Lithium Ion Batteries (LIBs). Regarding aging processes, quantitative analyses are important to evaluate the magnitude of a certain process for the total capacity decrease. The challenge for the investigation of aged battery materials is the lack of reference materials such that techniques based on them cannot be applied. With the use of reference sample-free quantitative X-ray fluorescence analysis (XRF), we investigated the total mass deposition of manganese deposited at the anode for an aged cell. For 50 full cycles with elevated cut-off voltage, the capacity decreased by 12.5%, while up to 1.6‰ of cathodic manganese was found deposited in the anode. Furthermore, the species of manganese deposited in the anode has been studied with near-edge X-ray absorption fine structure analysis (NEXAFS) at the manganese L-edges and K-edges. In addition to a different discrimination capability at L- and K-edges, the application of significantly different excitation energies provides sensitivity to different sample depths. We determined the manganese deposition to be in di- and tetra-valent states, whereby tetravalent manganese is solely found in the anode bulk. The combination of the different methods generates a clearer understanding of the chemical processes in the battery and can therefore help to improve the performance by exploring the absolute mass deposition and the electronic structure of elements contained in enhanced material combinations.

Quantitative chemical analysis of airborne particulate matter (PM) is vital for the understanding of health effects in indoor and outdoor environments, as well as for enforcing EU air quality regulations. Typically, airborne particles are sampled over long time periods on filters, followed by lab-based analysis, e.g., with inductively coupled plasma mass spectrometry (ICP-MS). During the EURAMET EMPIR AEROMET project, cascade impactor aerosol sampling is combined for the first time with on-site total reflection X-ray fluorescence (TXRF) spectroscopy to develop a tool for quantifying particle element compositions within short time intervals and even on-site. This makes variations of aerosol chemistry observable with time resolution only a few hours and with good size resolution in the PM10 range. The study investigates the proof of principles of this methodological approach. Acrylic discs and silicon wafers are shown to be suitable impactor carriers with sufficiently smooth and clean surfaces, and a non-destructive elemental mass concentration measurement with a lower limit of detection around 10 pg/m3 could be achieved. We demonstrate the traceability of field TXRF measurements to a radiometrically calibrated TXRF reference, and the results from both analytical methods correspond satisfactorily.

In this work, we present a grazing incidence X-ray diffraction study of the surface of a 0.24Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) [011] poled rhombohedral single crystal. The near surface microstructure (the top several tens to hundreds of unit cells) was measured in situ under an applied electric field. The strains calculated from the change in lattice parameters have been compared to the macroscopic strain measured with a strain gauge affixed to the sample surface. The depth dependence of the electrostrain at the crystal surface was investigated as a function of temperature. The analysis revealed hidden sweet spots featuring unusually high strains that were observed as a function of depth, temperature and orientation of the lattice planes.

We present valence-to-core x-ray emission spectroscopy of Ti, TiO and TiO2 by means of a double crystal von Hamos spectrometer based on full-cylinder highly-annealed pyrolytic graphite mosaic crystals. We demonstrate that, using a double crystal configuration, an energy resolution of E/ΔE ≈ 2700 can be achieved in a compact setup using cylindrically curved optics with a radius of curvature of 50 mm. The stated energy resolution proved to be high enough to identify and determine chemical shifts of the Kβ2,5 and Kβ" emission lines of both oxides. The experimental results are supported by calculations with the ab initio package OCEAN and compared to literature values.

Herein we report on the hydrolysis mechanism of [Pt{N(p-HC 6 F 4 )CH 2 } 2 (NC 5 H 5 ) 2 (OH) 2 ], a platinum(IV) complex that exhibits anti-cancer properties. Atomic telemetry, an in situ technique based on electron structure sensitive X-ray spectroscopy, revealed that hydrolysis preceded any reduction of the metal center. The obtained results are complemented with 19 F NMR measurements and theoretical calculations and support the observation that this Pt IV complex does not reduce spontaneously to Pt II in HEPES buffer solution at pH 7.4 and after 24 h incubation. These results are of importance for the design of novel Pt-based coordination complexes as well as understanding their behavior under physiological conditions.

Herein, we report a systematic study on the electronic structure of surface and bulk TiO2 doped with C, N or S. The results were attained with a semi-empirical method consisting of a combination between resonant X-ray emission spectroscopy (RXES) measurements and localized density of states (LDOS) simulations. Experimental TiO2 RXES data was used to fit FEFF code empirical parameters, and subsequently frozen for the theoretical analysis of LDOS of TiO2 doped materials. The results show significant electronic structure differences between bulk and surface doping, as well as in the nearest Ti atom electronic structure if it is located at the surface or sub-surface, with potential consequences to the photo-catalytic process. The methodology can be adapted to study other dopants, morphologies, structures and surface terminations and as well as other inorganic semiconductors.

Knowledge on the temporal and size distribution of particulate matter (PM) in air as well as on its elemental composition is a key information for source appointment, for the investigation of their influence on environmental processes and for providing reliable data for climate models. While cascade impactors allow for time- and size-resolved collection of airborne PM, total reflection X-ray fluorescence (TXRF) allows for element-sensitive investigation of minute sample amounts thanks to its detection sensitivity. But during quantification by means of TXRF it is crucial to be aware of the linear calibration limits of TXRF in order to identify situations where collection times or pollution levels in the different size partitions were exceedingly long or high. Indeed, TXRF can only be reliably used when the amount of matter collected on the top of the substrate is sufficiently small. By means of grazing incidence X-ray fluorescence (GIXRF), where the excitation conditions are varied in a controlled and reliable manner and include also the TXRF regime, a self consistent quantification of elemental mass depositions can be performed in order to validate or falsify TXRF quantification results. For low mass depositions an agreement within a few percent for the different excitation conditions was found, while for increasing amounts of material relative errors of up to a factor of 4 were found for TXRF as compared to GIXRF. Thus, TXRF cannot be applied to all samples regardless of their coverage and threshold values for the validity of quantification results need to be determined. As a flexible solution, GIXRF allows extending the dynamic range of reliably quantifiable mass depositions beyond the linear regime of TXRF, an important advantage when variable amounts of airborne PM need to be quantified as in the case of collection with cascade impactors. The presented more reliable quantification approach can be transferred to mobile tabletop instrumentation as well. This aspect is highly relevant for air quality monitoring in terms of supporting the introduction of appropriate legislation and measures for health and climate protection as well as for supporting their enforcement.

In the present work high energy resolution off-resonant X-ray spectroscopy (HEROS) was employed at a synchrotron to study a silica supported Ta(V) bisalkyl catalyst activated in hydrogen. The Ta L α 1 HEROS spectra were measured during oxidation of the starting complex and the relative species’ concentration was successfully retrieved as a function of time using the fingerprint HEROS spectra measured for the unoxidized and the oxidized catalyst. Based on the experimental data and theory-based calculations, it was shown that oxidation of the active Ta catalyst leads to the formation of mono- and di-meric species on the SiO2 surface. The obtained results were compared to those of the previously reported time-resolved HEROS study on an inactive silica supported Ta(V) bisalkyl catalyst’s concentration evolution during its oxidation Blachucki et al. (2015). The study allowed observation of an immediate transition of the active Ta catalyst from its unoxidized form to the oxidized one. This finding is dissimilar to the result of the study on the inactive Ta catalyst, where the oxidation led through an intermediate step.

We review the high energy resolution off-resonant spectroscopy (HEROS) technique. HEROS probes the unoccupied electronic states of matter in a single-shot manner thanks to the combination of off-re ...

We present experimental and theoretical X-ray emission spectroscopy (XES) data of the Fe Kβ line for Iron(II)sulfide (FeS) and Iron(II)disulfide (FeS(2)). In comparison to X-ray absorption spectroscopy (XAS), XES offers different discrimination capabilities for chemical speciation, depending on the valence states of the compounds probed and, more importantly in view of a a broader, laboratory-based use, a larger flexibility with respect to the excitation source used. The experimental Fe Kβ XES data was measured using polychromatic X-ray radiation and a compact full-cylinder von Hamos spectrometer while the calculations were realized using the OCEAN code. The von Hamos spectrometer used is characterized by an energy window of up to 700 eV and a spectral resolving power of E/ΔE = 800. The large energy window at a single position of the spectrometer components is made profit of to circumvent the instrumental sensitivity of wavelength-dispersive spectrometers to sample positioning. This results in a robust energy scale which is used to compare experimental data with ab initio valence-to-core calculations, which are carried out using the ocean package. To validate the reliability of the ocean package for the two sample systems, near edge X-ray absorption fine structure measurements of the Fe K absorption edge are compared to theory using the same input parameters as in the case of the X-ray emission calculations. Based on the example of iron sulfide compounds, the combination of XES experiments and ocean calculations allows unravelling the electronic structure of different transition metal sulfides and qualifying XES investigations for the speciation of different compounds.

In this work, Pt-Ti core-shell nanoparticles (NP) of 2 nm to 3 nm in size and 30000 u \pm 1500 u as specified single particle mass, deposited on flat silicon substrates by means of a mass-selected cluster beam source, were used for the investigation of the modification of the X-Ray Standing Wave (XSW) field intensity with increasing NP surface coverage. The focus of the investigation is on the determination of the range of validity of the undisturbed flat surface approach of the XSW intensity in dependence of the actual coverage rate of the surface. Therefore, the nanoparticles were characterized using reference-free grazing incidence X-ray fluorescence analysis (GIXRF) employing radiometrically calibrated instrumentation. In addition, near-edge X-ray absorption fine structure (NEXAFS) measurements were performed to investigate the binding state of titanium in the core-shell nanoparticles which was found to be amorphous TiO2. The combination of GIXRF measurements and of the calculated XSW field intensities allow for a quantification of the core-shell nanoparticle surface coverage. For six different samples, the peak surface coverage could be determined to vary from 7 % to 130 % of a complete monolayer-equivalent coverage. A result of the current investigation is that core-shell nanoparticles modify the intensity distribution of the XSW field with increasing surface coverage. This experimental result is in line with calculated XSW field intensity distributions at different surface coverages using an effective density approach., Comment: 19 pages, 8 figures and 3 tables

The enhancement factor (EF) is an essential parameter in the field of surface-enhanced Raman spectroscopy (SERS), indicating the magnification of the Raman signal of molecules interacting with the surface of plasmonic nanostructures. The calculation of EF requires a careful evaluation of both the signal intensities and the number of molecules in SERS and normal Raman conditions. The determination of the surface density of molecules adsorbed on the plasmonic substrate is a challenging task, but essential for the estimation of the number of SERS-active molecules. This paper describes the determination of EF using 7-mercapto-4-methylcoumarin (MMC) as the probe molecule on gold-coated silicon nanowires, integrating SERS and normal Raman spectroscopy with X-ray fluorescence (RF-XRF) data that provide a reference-free quantitative measurement of the molecular surface density. In addition, the surface coverage of MMC on the substrate is modelled by molecular mechanics (MM) and molecular dynamics (MD) simulations.

LiMn 2O 4 is a promising candidate for a cathode material in lithium-ion batteries because of its ability to intercalate lithium ions reversibly through its three-dimensional manganese oxide network. One of the promising techniques for depositing LiMn 2O 4 thin-film cathodes is atomic layer deposition (ALD). Because of its unparalleled film thickness control and film conformality, ALD helps to fulfill the industry demands for smaller devices, nanostructured electrodes, and all-solid-state batteries. In this work, the intercalation mechanism of Li + ions into an ALD-grown β-MnO 2 thin film was studied. Samples were prepared by pulsing LiO tBu and H 2O for different cycle numbers onto about 100 nm thick MnO 2 films at 225 °C and characterized with X-ray absorption spectroscopy, X-ray diffraction, X-ray reflectivity, time-of-flight elastic recoil detection analysis, and residual stress measurements. It is proposed that for tBu/H 2O, the Li + ions penetrate only to the surface region of the β-MnO 2 film, and the samples form a mixture of β-MnO 2 and a lithium-deficient nonstoichiometric spinel phase Li xMn 2O 4 (0 < x < 0.5). When the lithium concentration exceeds x ≈ 0.5 in Li xMn 2O 4 (corresponding to 100 cycles of LiO tBu/H 2O), the crystalline phase of manganese oxide changes from the tetragonal pyrolusite to the cubic spinel, which enables the Li + ions to migrate throughout the whole film. Annealing in N 2 at 600 °C after the lithium incorporation seemed to convert the films completely to the pure cubic spinel LiMn 2O 4.

We present valence-to-core x-ray emission spectroscopy of Ti, TiO and TiO

Angle‐resolved X‐ray fluorescence spectroscopy gives access to elemental analysis of nanoscaled materials. The two main techniques of this method are grazing incidence X‐ray fluorescence (GIXRF) and grazing emission X‐ray fluorescence (GEXRF) spectroscopy. Principles of both techniques including main applications are discussed in this Review. The main focus lies on the description of GEXRF technique and its new analytical possibilities in the nano‐world.

"Probe-before-destroy" methodology permitted diffraction and imaging measurements of intact specimens using ultrabright but highly destructive X-ray free-electron laser (XFEL) pulses. The methodology takes advantage of XFEL pulses ultrashort duration to outrun the destructive nature of the X-rays. Atomic movement, generally on the order of >50 fs, regulates the maximum pulse duration for intact specimen measurements. In this contribution, we report the electronic structure damage of a molecule with ultrashort X-ray pulses under preservation of the atoms' positions. A detailed investigation of the X-ray induced processes revealed that X-ray absorption events in the solvent produce a significant number of solvated electrons within attosecond and femtosecond timescales that are capable of coulombic interactions with the probed molecules. The presented findings show a strong influence on the experimental spectra coming from ionization of the probed atoms' surroundings leading to electronic structure modification much faster than direct absorption of photons. This work calls for consideration of this phenomenon in cases focused on samples embedded in, e.g., solutions or in matrices, which in fact concerns most of the experimental studies.

The geometry of a Si$_3$N$_4$ lamellar grating was investigated experimentally with reference-free grazing-incidence X-ray fluorescence analysis. While simple layered systems are usually treated with the matrix formalism to determine the X-ray standing wave field, this approach fails for laterally structured surfaces. Maxwell solvers based on finite elements are often used to model electrical field strengths for any 2D or 3D structures in the optical spectral range. We show that this approach can also be applied in the field of X-rays. The electrical field distribution obtained with the Maxwell solver can subsequently be used to calculate the fluorescence intensities in full analogy to the X-ray standing wave field obtained by the matrix formalism. Only the effective 1D integration for the layer system has to be replaced by a 2D integration of the finite elements, taking into account the local excitation conditions. We will show that this approach is capable of reconstructing the geometric line shape of a structured surface with high elemental sensitivity. This combination of GIXRF and finite-element simulations paves the way for a versatile characterization of nanoscale-structured surfaces.

ECS journal of solid state science and technology 7(7), Q3108-Q3113 (2018). doi:10.1149/2.0171807jss special issue: "JSS Focus Issue on Semiconductor-Based Sensors for Application to Vapors, Chemicals, Biological Species, and Medical Diagnosis", Published by ECS, Pennington, NJ

The potential of valence to core Al X-ray emission spectroscopy to determine aluminum distribution in ferrierite zeolites was investigated. The recorded emission spectra of four samples prepared with different structure directing agents exhibit slight variations in the position of the main emission peak and the intensity of its low energy shoulder. Theoretical calculations indicate that an increased intensity of the Kβx shoulder in the Al emission spectra can be linked to a predominant occupation of the T3 site by a single aluminum atom. This study thus suggests that valence to core X-ray emission spectroscopy can be applied to help determine the occupation of aluminum at crystallographic T-sites in zeolites.

We report on studies of state-populations during the two-photon absorption process using intense X-ray pulses. The calculations were performed in a time-dependent manner using a simple three-level model expressed by coupled rate equations. We show that the proposed approach describes well the measured rates of X-rays excited in the one-photon and two-photon absorption processes, and allows detailed investigation of the state population dynamics during the course of the incident X-ray pulse. Finally, we demonstrate that the nonlinear interaction of X-ray pulses with atoms leads to a time-narrowing of state populations. This narrowing-effect is attributed to a quadratic incidence X-ray intensity dependence characteristic for nonlinear interactions of photons with matter.

FeNi Hydroxides (FeNi-HD) have been considered as promising substitutes to noble metal electrocatalysts for oxygen evolution reaction (OER). In this work, we design and realize FeNi-HD nanotube arrays (FeNi-HDNAs) on Ni foam via an in-situ reaction and Kirkendall effect. The obtained catalysts possess higher specific surface area, more catalytic active sites and better chemical stability for OER. Electron migrations from the Fe 3d orbitals to Ni sites in the FeNi-HDNAs lead to more unoccupied Fe 3d states and a higher oxidation state. As expected, FeNi-HDNAs exhibit lower overpotential as well as lower Tafel slope and better durability than the Fe- or Ni-HD peers. DFT calculations elucidate that FeNi hydroxides lower the energy barrier of rate-determining step in OER. Moreover, a high current density of 10 mA cm−2 is obtained at a low potential of 1.49 V using FeNi-HDNAs as the bifunctional electrocatalyst for overall water splitting in basic solution.

In this work the complete L-emission spectrum of gadolinium with respect to line energies, natural line widths, and relative transition probabilities was investigated using monochromatized synchrotron radiation. The measurements were realized in the PTB laboratory at BESSY II by means of an in-house built von Hamos spectrometer based on up to two full-cylinder HAPG mosaic crystal. The von Hamos spectrometer is calibrated by means of elastically scattered photons from the employed synchrotron radiation beamline leading to a well-defined energy scale and an experimentally determined spectrometer response. A selective excitation of the gadolinium L subshells was carried out to ensure a robust deconvolution of neighboring emission lines of different L subshells. The experimental results are discussed in the context of existing data from common databases and published values since significant deviations, especially for the L$\gamma_2$ and L$\gamma_3$ emission lines, are observed. We further substantiate and discuss two satellite lines at the low-energy side of the L$\beta_{2,15}$ and L$\gamma_1$ emission lines arising from the N$_{4,5}$ subshell.

The two novel manganese( II ) complexes with 2-hydroxymethylpyridine (2-CH 2 OHpy) {[Mn 2 ( μ -Cl) 2 - (2-CH 2 OHpy) 4 ]Cl 2 ·2H 2 O( 1 )} and 2-hydroxyethylpyridine (2-(CH 2 ) 2 OHpy) {[Mn(2-(CH 2 ) 2 OHpy) 2 (NCS) 2 ]( 2 )} were synthesized and characterized by means of X-ray di ff raction, IR, EPR, HF EPR spectroscopy, mag- netic and TG/DTG data. The complexes show catalase-like activity in neutral aqueous solution since they were able to disproportionate H_{2}O_{2} to harmless H_{2}O and O_{2} . Both complexes act as true catalysts since they reverted to their original form after depleting all the H_{2}O_{2} , as suggested by the operando resonant inelastic X-ray spectroscopy (RIXS) measurements.

The grazing emission X-ray fluorescence (GEXRF) technique was applied to the analysis of different Al films, with nominal thicknesses in the range of 1 nm to 150 nm, on Si wafers. In GEXRF the sample volume from which the fluorescence intensity is detected is restricted to a near-surface region whose thickness can be tuned by varying the observation angle. This is possible because of the refraction of the fluorescence X-rays and the quite long emission paths within the probed sample. By recording the X-ray fluorescence signal for different shallow emission angles, defined relatively to the flat, smooth sample surface, the deposited Al surface layers of the different samples could be well characterized in terms of layer thickness, layer density, oxidation and surface roughness. The advantages offered by synchrotron radiation and the employed wavelength-dispersive detection setup were profited from. The GEXRF results retrieved were confirmed by complementary measurements. The experimental setup, the principles and advantages of GEXRF and the analysis of the recorded angular intensity profiles will be discussed in details.

The lack of molecular mechanistic understanding of the interaction between metal complexes and biomolecules hampers their potential medical use. Herein we present a robust procedure combining resonant X-ray emission spectroscopy and multiscale molecular dynamics simulations, which allows for straightforward elucidation of the precise interaction mechanism at the atomic level. The report unveils an unforeseen hydrolysis process and DNA binding of [Pt{N(p-HC6F4)CH2}2py2] (Pt103), which showed potential cytotoxic activity in the past. Pt103 preferentially coordinates to adjacent adenine sites, instead of guanine sites as in cisplatin, because of its hydrogen bond ability. Comparison with previous research on cisplatin suggests that selective binding to guanine or adenine may be achieved by controlling the acidity of the compound.