High-Resolution X-ray Photoelectron Spectroscopy of an IrO2(110) Film on Ir(100).

High-resolution X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) were used to characterize IrO2(110) films on Ir(100) with stoichiometric as well as OH-rich terminations. Core-level Ir 4f and O 1s peaks were identified for the undercoordinated Ir and O atoms and bridging and on-top OH groups at the IrO2(110) surfaces. Peak assignments were validated by comparison of the core-level shifts determined experimentally with those computed using DFT, quantitative analysis of the concentrations of surface species, and the measured variation of the Ir 4f peak intensities with photoelectron kinetic energy. We show that exposure of the IrO2(110) surface to O2 near room temperature produces a large quantity of on-top OH groups because of reaction of background H2 with the surface. The peak assignments made in this study can serve as a foundation for future experiments designed to utilize XPS to uncover atomic-level details of the surface chemistry of IrO2(110).

An electrochemical cell for 2-dimensional surface optical reflectance during anodization and cyclic voltammetry.

We have developed an electrochemical cell for in situ 2-Dimensional Surface Optical Reflectance (2D-SOR) studies during anodization and cyclic voltammetry. The 2D-SOR signal was recorded from electrodes made of polycrystalline Al, Au(111), and Pt(100) single crystals. The changes can be followed at a video rate acquisition frequency of 200 Hz and demonstrate a strong contrast between oxidizing and reducing conditions. Good correlation between the 2D-SOR signal and the anodization conditions or the cyclic voltammetry current is also observed. The power of this approach is discussed, with a focus on applications in various fields of electrochemistry. The combination of 2D-SOR with other techniques, as well as its spatial resolution and sensitivity, has also been discussed.

Combining high-energy X-ray diffraction with Surface Optical Reflectance and Planar Laser Induced Fluorescence for operando catalyst surface characterization.

We have combined three techniques, High Energy Surface X-Ray Diffraction (HESXRD), Surface Optical Reflectance, and Planar Laser Induced Fluorescence in an operando study of CO oxidation over a Pd(100) catalyst. We show that these techniques provide useful new insights such as the ability to verify that the finite region being probed by techniques such as HESXRD is representative of the sample surface as a whole. The combination is also suitable to determine when changes in gas composition or surface structure and/or morphology occur and to subsequently correlate them with high temporal resolution. In the study, we confirm previous results which show that the Pd(100) surface reaches high activity before an oxide can be detected. Furthermore, we show that the single crystal catalyst surface does not behave homogeneously, which we attribute to the surface being exposed to inhomogeneous gas conditions in mass transfer limited scenarios.

Surface development of a brazing alloy during heat treatment-a comparison between UHV and APXPS.

In an attempt to bridge the pressure gap, APXPS was used to follow the surface development of an aluminum brazing sheet during heating in an ambient oxygen-pressure mimicking the environment of an industrial brazing furnace. The studied aluminum alloy brazing sheet is a composite material consisting of two aluminum alloy standards whose surface is covered with a native aluminum oxide film. To emphasize the necessity of studies of this system in ambient sample environments it is compared to measurements in UHV. Changes in thickness and composition of the surface oxide were followed after heating to 300 °C, 400 °C, and 500 °C. The two sets presented in this paper show that the surface development strongly depends on the environment the sample is heated in.

One mutation, two distinct disease variants: unravelling the impact of transthyretin amyloid fibril composition.

Although hereditary transthyretin (h-ATTR) amyloidosis is a monogenetic disease, a large variation in its phenotype has been observed. The common hypothesis of amyloid fibril formation involves dissociation of the transthyretin (TTR) tetramer into monomers that after misfolding reassemble into amyloid fibrils. This notion is partly challenged by the finding of two distinct types of amyloid fibrils. One of these, type A, consists of C-terminal ATTR fragments and full-length TTR, whereas the other, type B, consists only of full-length TTR. All organs of an individual patient contain ATTR deposits of either type A or type B fibrils, and the composition in each individual remains unchanged over time. The finding of two distinct types of ATTR fibrils suggests that there are at least two different pathways in operation for ATTR fibril formation. For the most common European mutation, TTR Val30Met, ATTR fibril composition is related to the outcome of liver transplantation, which is the first successful treatment for the disease, and the penetrance of the trait. In addition, the presence of C-terminal ATTR fragments has an impact on the affinity for various tracers used for noninvasive imaging of amyloid depositions such as 99 m-technetium-diphosphono-propanodicarboxylic acid scintigraphy and positron emission tomography utilizing Pittsburgh component B, and even for the gold standard diagnostic procedure, tissue biopsy stained by Congo red and examined under polarized light. The importance of amyloid fibril composition needs to be taken into consideration when designing clinical trials of treatment modalities, and also in the evaluation of diagnostic methods such as imaging techniques.

Atomic scale surface structure and morphology of InAs nanowire crystal superlattices: the effect of epitaxial overgrowth.

While shell growth engineering to the atomic scale is important for tailoring semiconductor nanowires with superior properties, a precise knowledge of the surface structure and morphology at different stages of this type of overgrowth has been lacking. We present a systematic scanning tunneling microscopy (STM) study of homoepitaxial shell growth of twinned superlattices in zinc blende InAs nanowires that transforms {111}A/B-type facets to the nonpolar {110}-type. STM imaging along the nanowires provides information on different stages of the shell growth revealing distinct differences in growth dynamics of the crystal facets and surface structures not found in the bulk. While growth of a new surface layer is initiated simultaneously (at the twin plane interface) on the {111}A and {111}B nanofacets, the step flow growth proceeds much faster on {111}A compared to {111}B leading to significant differences in roughness. Further, we observe that the atomic scale structures on the {111}B facet is different from its bulk counterpart and that shell growth on this facet occurs via steps perpendicular to the ⟨112⟩B-type directions.

Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules.

Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.

High-energy surface X-ray diffraction for fast surface structure determination.

Understanding the interaction between surfaces and their surroundings is crucial in many materials-science fields, such as catalysis, corrosion, and thin-film electronics, but existing characterization methods have not been capable of fully determining the structure of surfaces during dynamic processes, such as catalytic reactions, in a reasonable time frame. We demonstrate an x-ray-diffraction-based characterization method that uses high-energy photons (85 kiloelectron volts) to provide unexpected gains in data acquisition speed by several orders of magnitude and enables structural determinations of surfaces on time scales suitable for in situ studies. We illustrate the potential of high-energy surface x-ray diffraction by determining the structure of a palladium surface in situ during catalytic carbon monoxide oxidation and follow dynamic restructuring of the surface with subsecond time resolution.

A high pressure x-ray photoelectron spectroscopy study of CO oxidation over Rh(100).

We have studied the oxidation of CO over Rh(100) using high pressure x-ray photoelectron spectroscopy under CO and O2 pressures ranging from 0.01 to 1 mbar. The results show a very low or no conversion for the CO covered surface found at low temperatures, while the activity rises slightly when the temperature is high enough for some CO to desorb, exposing surface sites for dissociative O2 adsorption. As the temperature is increased further, more CO desorbs and oxygen replaces CO as the dominating species at the surface. At the same time we find a sudden increase in the reactivity, such that all CO that reaches the surface is instantly transformed into CO2. We find that the O coverage in the active state is highly dependent on the total pressure and, although we do not detect any presence of a surface oxide as in previous surface x-ray diffraction studies, the highest O coverage indicates that the surface is close to being oxidized.

Direct imaging of atomic scale structure and electronic properties of GaAs wurtzite and zinc blende nanowire surfaces.

Using scanning tunneling microscopy and spectroscopy we study the atomic scale geometry and electronic structure of GaAs nanowires exhibiting controlled axial stacking of wurtzite (Wz) and zinc blende (Zb) crystal segments. We find that the nonpolar low-index surfaces {110}, {101[overline]0}, and {112[overline]0} are unreconstructed, unpinned, and without states in the band gap region. Direct comparison between Wz and Zb GaAs reveal a type-II band alignment and a Wz GaAs band gap of 1.52 eV.

In situ x-ray photoelectron spectroscopy of model catalysts: at the edge of the gap.

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO(2) production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

Formation and structure of graphene waves on Fe(110).

A very rich Fe-C phase diagram makes the formation of graphene on iron surfaces a challenging task. Here we demonstrate that the growth of graphene on epitaxial iron films can be realized by chemical vapor deposition at relatively low temperatures, and that the formation of carbides can be avoided in excess of the carbon-containing precursors. The resulting graphene monolayer creates a novel periodically corrugated pattern on Fe(110). Using low-energy electron microscopy and scanning tunneling microscopy, we show that it is modulated in one dimension forming long waves with a period of ∼4 nm parallel to the [001] direction of the substrate, with an additional height modulation along the wave crests. The observed topography of the graphene/Fe superstructure is well reproduced by density functional theory calculations, and found to result from a unique combination of the lattice mismatch and strong interfacial interaction, as probed by core-level photoemission and x-ray absorption spectroscopy.

An in situ set up for the detection of CO2 from catalytic CO oxidation by using planar laser-induced fluorescence.

We report the first experiment carried out on an in situ setup, which allows for detection of CO(2) from catalytic CO oxidation close to a model catalyst under realistic reaction conditions by the means of planar laser-induced fluorescence (PLIF) in the mid-infrared spectral range. The onset of the catalytic reaction as a function of temperature was followed by PLIF in a steady state flow reactor. After taking into account the self-absorption of CO(2), a good agreement between the detected CO(2) fluorescence signal and the CO(2) mass spectrometry signal was shown. The observed difference to previously measured onset temperatures for the catalytic ignition is discussed and the potential impact of IR-PLIF as a detection technique in catalysis is outlined.

The Rh(100)-(3 × 1)-2O structure.

The O adsorption on Rh(100) has been studied using high resolution core level spectroscopy, low energy electron diffraction and scanning tunnelling microscopy. In addition to the well known (2 × 2), (2 × 2)-pg and c(8 × 2) structures at coverages of 0.25, 0.5 and 1.75 ML respectively, an intermediate (3 × 1) structure with a coverage of 2/3 ML is identified.

One-dimensional corrugation of the h-BN monolayer on Fe(110).

We report on a new nanopatterned structure represented by a single atomic layer of hexagonal boron nitride (h-BN) forming long periodic waves on the Fe(110) surface. The growth process and the structure of this system are characterized by X-ray absorption (XAS), core-level photoemission spectroscopy (CL PES), low-energy electron microscopy (LEEM), microbeam low-energy electron diffraction (µLEED), and scanning tunneling microscopy (STM). The h-BN monolayer on Fe(110) is periodically corrugated in a wavy fashion with an astonishing degree of long-range order, periodicity of 2.6 nm, and the corrugation amplitude of ∼0.8 Å. The wavy pattern results from a strong chemical bonding between h-BN and Fe in combination with a lattice mismatch in either [111] or [111] direction of the Fe(110) surface. Two primary orientations of h-BN on Fe(110) can be observed corresponding to the possible directions of lattice match between h-BN and Fe(110), with approximately equal area of the boron nitride domains of each orientation.

The Active Phase of Palladium during Methane Oxidation.

The active phase of Pd during methane oxidation is a long-standing puzzle, which, if solved, could provide routes for design of improved catalysts. Here, density functional theory and in situ surface X-ray diffraction are used to identify and characterize atomic sites yielding high methane conversion. Calculations are performed for methane dissociation over a range of Pd and PdOx surfaces and reveal facile dissociation on either under-coordinated Pd sites in PdO(101) or metallic surfaces. The experiments show unambiguously that high methane conversion requires sufficiently thick PdO(101) films or metallic Pd, in full agreement with the calculations. The established link between high activity and atomic structure enables rational design of improved catalysts.

Surface structure and reactivity of Pd(100) during CO oxidation near ambient pressures.

The surface structure of Pd(100) during CO oxidation was measured using a combination of a flow reactor and in situ surface X-ray diffraction coupled to a large-area 2-dimensional detector. The surface structure was measured for P(O(2))/P(CO) ratios between 0.6 and 10 at a fixed total gas pressure of 200 mbar and a fixed CO pressure of 10 ± 1 mbar. In conjunction with the surface structure the reactivity of the surface was also determined. For all P(O(2))/P(CO) ratios the surface was found to oxidize above a certain temperature. Three different types of oxides were observed: the surface oxide, an epitaxial layer of bulk-like PdO, and a non-epitaxial layer of bulk-like PdO. As soon as an oxide was present the reactivity of the surface was found to be mass transfer limited by the flux of CO molecules reaching the surface.

Short adult stature and overweight are associated with poor intellectual performance in subjects born preterm.

BACKGROUND/AIMS: To study the association between preterm birth and adult intellectual performance, with special emphasis on the influence of postnatal growth. METHODS: A population-based cohort study was performed on 272,046 males, born between 1973 and 1978, of whom 248,447 were conscripted for military service between 1991 and 1997. Birth characteristics were obtained from the Swedish Medical Birth Register and information on intellectual performance, final height and BMI were taken from the Swedish Conscript Register. Multiple logistic regression analysis was performed. RESULTS: At conscription, males born preterm had lower results at tests of intellectual performance compared to those born at term. Short adult stature among these males enhanced the risk of low intellectual performance, as compared to those with normal adult stature. Moreover, a high adult BMI in the males born preterm was associated with an increased risk of subnormal performance as compared to those with normal BMI. CONCLUSIONS: Subjects born preterm had poorer intellectual performance than those born at term. Short adult stature or a high BMI was associated with an even higher risk for poor intellectual performance in the subjects born preterm. This indicates the occurrence of common mechanisms underlying growth and cognitive development.

Impact of oxygen coadsorption on intercalation of cobalt under the h-BN nanomesh.

The process of penetration of cobalt atoms through the h-BN nanomesh on Rh(111) is investigated with both spectroscopic and microscopic techniques. It is discovered that oxygen coadsorption can drastically modify the physical properties and behavior of the deposited Co clusters upon postannealing. In the absence of oxygen, Co forms small nanoparticles in the pores (bonding parts) of the h-BN nanomesh, which start to agglomerate at elevated temperatures without any considerable intercalation. However, even a tiny amount of coadsorbed oxygen reduces cobalt agglomeration and greatly promotes its intercalation and trapping under h-BN. The oxygen exposure necessary for a complete intercalation of 1-2 monolayers of Co is very low, and the formation of oxidic species can be easily avoided. The nanomesh structure remains intact upon intercalating submonolayer amounts of Co, while further intercalation gradually distorts and finally destroys the periodic corrugation. Fortunately, this process is not accompanied by damaging the h-BN sheet itself, and the original structure can be restored by removing Co upon annealing at higher temperatures.

Direct observation of atomic scale surface relaxation in ortho twin structures in GaAs by XSTM.

We have studied the (110) GaAs surface of a structure containing ortho twins by cross-sectional scanning tunnelling microscopy and we have compared the experimental results with ab initio density functional theory calculations and STM simulations. Both experimentally and theoretically we find that the surface of different twin crystallites are significantly displaced with respect to each other, parallel to the twin boundary. This result is explained by a surface relaxation of the atoms in the (110) GaAs surface and the difference between the atomic configuration of the ortho twins.