Operando atomic structure and active sites of TiO2(110)-supported gold nanoparticles during carbon monoxide oxidation

International audienceIt is well known that gold nanoparticles supported on TiO2 act as a catalyst for CO oxidation, even below room temperature. Despite extensive studies, the origin of this catalytic activity remains under debate. Indeed, when the particle size decreases, many changes may occur; thus modifying the nanoparticles' electronic properties and consequently their catalytic performances. Thanks to a state-of-the-art home-developed setup, model catalysts can be prepared in ultra-high vacuum and their morphology then studied in operando conditions by Grazing Incidence Small Angle X-ray Scattering, as well as their atomic structure by Grazing Incidence X-ray Diffraction as a function of their catalytic activity. We previously reported on the existence of a catalytic activity maximum observed for three-dimensional gold nanoparticles with a diameter of 2-3 nm and a height of 6-7 atomic planes. In the present work we correlate this size dependence of the catalytic activity to the nanoparticles' atomic structure. We show that even when their size decreases below the optimum diameter, the gold nanoparticles keep the face-centered cubic structure characteristic of bulk gold. Nevertheless, for these smallest nanoparticles, the lattice parameter presents anisotropic strains with a larger contraction in the direction perpendicular to the surface. Moreover a careful analysis of the atomic-scale morphology around the catalytic activity maximum tends to evidence the role of sites with a specific geometry at the interface between the nanoparticles and the substrate. This argues for models where atoms at the interface periphery act as catalytically active sites for carbon monoxide oxidation

New reactor dedicated to in operando studies of model catalysts by means of surface x-ray diffraction and grazing incidence small angle x-ray scattering

International audienceA new experimental setup has been developed to enable in situ studies of catalyst surfaces during chemical reactions by means of surface x-ray diffraction (SXRD) and grazing incidence small angle x-ray scattering. The x-ray reactor chamber was designed for both ultrahigh-vacuum (UHV) and reactive gas environments. A laser beam heating of the sample was implemented; the sample temperature reaches 1100 K in UHV and 600 K in the presence of reactive gases. The reactor equipment allows dynamical observations of the surface with various, perfectly mixed gases at controlled partial pressures. It can run in two modes: as a bath reactor in the pressure range of 1-1000 mbars and as a continuous flow cell for pressure lower than 10−3 mbar. The reactor is connected to an UHV preparation chamber also equipped with low energy electron diffraction and Auger spectroscopy. This setup is thus perfectly well suited to extend in situ studies to more complex surfaces, such as epitaxial films or supported nanoparticles. It offers the possibility to follow the chemically induced changes of the morphology, the structure, the composition, and growth processes of the model catalyst surface during exposure to reactive gases. As an example the Pd8Ni92(110) surface structure was followed by SXRD under a few millibars of hydrogen and during butadiene hydrogenation while the reaction was monitored by quadrupole mass spectrometry. This experiment evidenced the great sensitivity of the diffracted intensity to the subtle interaction between the surface atoms and the gas molecules

Simulation of surface resonant x-ray diffraction

We present an ab initio numerical tool to simulate surface resonant X-ray diffraction experiments. The crystal truncation rods and the spectra around a given X-ray absorption edge are calculated at any position of the reciprocal space. Density functional theory is used to determine the resonant scattering factor of an atom within its local environment and to calculate the diffraction peak intensities for surfaces covered with a thin film or with one or several adsorbed layers. Besides the sample geometry, the collected data also depend on several parameters, such as beam polarization and incidence and exit angles. In order to account for these factors, a numerical diffractometer mimicking the experimental operation modes has been created. Finally two case studies are presented in order to compare our simulations with experimental spectra: (i) a magnetite thin film deposited on a silver substrate and (ii) an electrochemical interface consisting of bromine atoms adsorbed on copper

Multiancestry analysis of the HLA locus in Alzheimer’s and Parkinson’s diseases uncovers a shared adaptive immune response mediated by HLA-DRB1*04 subtypes

Across multiancestry groups, we analyzed Human Leukocyte Antigen (HLA) associations in over 176,000 individuals with Parkinson’s disease (PD) and Alzheimer’s disease (AD) versus controls. We demonstrate that the two diseases share the same protective association at the HLA locus. HLA-specific fine-mapping showed that hierarchical protective effects of HLA-DRB1*04 subtypes best accounted for the association, strongest with HLA-DRB1*04:04 and HLA-DRB1*04:07, and intermediary with HLA-DRB1*04:01 and HLA-DRB1*04:03. The same signal was associated with decreased neurofibrillary tangles in postmortem brains and was associated with reduced tau levels in cerebrospinal fluid and to a lower extent with increased Aβ42. Protective HLA-DRB1*04 subtypes strongly bound the aggregation-prone tau PHF6 sequence, however only when acetylated at a lysine (K311), a common posttranslational modification central to tau aggregation. An HLA-DRB1*04-mediated adaptive immune response decreases PD and AD risks, potentially by acting against tau, offering the possibility of therapeutic avenues

Surfaces modèles or-palladium étudiées in situ:<br />de l'ultra-vide aux conditions de réactions catalytiques

Fundamental understanding of catalytic processes implies to correlate the atomic-scale structure of catalysts during a reaction with the macroscopic properties. This thesis work is in this frame and the main tool is the surface x-ray diffraction. An instrumental part is devoted to the development of a reactor which allows to characterise in situ the surfaces of model catalysts during a given reaction (up to 1 bar), by means of x-ray diffusion-based techniques. The main reactor features, as well as the first commissioning tests are described.A more fundamental part is dedicated to the study of bimetallic model surfaces based on gold and palladium with on one hand, gold deposits on Pd(110) and on the other hand, the (111) and (110) surfaces of the Au30Pd70 bulk alloy.The study of Au/Pd(110) in ultra-high vacuum has benefited from the complementarity between surface x-ray diffraction and scanning tunneling microscopy. For thicknesses up to 2.5 ML and annealing temperatures up to 470°C, the growth, structure and morphology of gold deposits are described.Finally, the study led on the Au30Pd70 bulk alloy has confirmed the interest of x-ray diffraction for characterising these model surfaces during a catalytic reaction. The structure of the (110) and (111) faces has been firstly studied in ultra-high vacuum and then during exposures at low pressures of hydrogen and oxygen (up to 10-5 mbar). Consecutively, the selective butadiene hydrogenation has been studied on the (111) surface, in the new reactor with the final aim to characterise the structure at different steps of the reaction. A strong effect of pure hydrogen on the volume and the surface of the alloy has been evidenced. These modifications are discussed in relation to the catalytic properties.La compréhension des processus catalytiques nécessite de pouvoir corréler la structure à l'échelle atomique des catalyseurs en cours de réaction avec les propriétés macroscopiques observées. Ce travail de thèse s'inscrit dans ce cadre et l'outil principal est la diffraction X de surface. Une partie instrumentale concerne le développement d'un réacteur permettant la caractérisation in situ, par des techniques de diffusion des rayons X, de surfaces de catalyseurs modèles pendant une réaction chimique donnée (jusqu'à 1 bar). Les caractéristiques principales du réacteur ainsi que les premiers tests de validation sous faisceau X sont décrits.En relation avec la problématique précédente, une partie plus fondamentale s'intéresse à l'étude de surfaces modèles bimétalliques à base d'or et de palladium avec d'une part, des dépôts d'or sur Pd(110) et d'autre part, les surfaces (111) et (110) d'un alliage massif Au30Pd70.L'étude du système Au/Pd(110), en ultra-vide, a bénéficié de la complémentarité entre la diffraction X de surface et la microscopie à effet tunnel. Pour des épaisseurs de dépôt jusqu'à 2.5 MC et des températures de recuit atteignant 470°C, nous nous sommes intéressés à la description de la croissance, de la structure et de la morphologie des dépôts d'or.L'étude menée sur l'alliage Au30Pd70 a confirmé l'intérêt de la diffraction X pour caractériser ces surfaces modèles au cours d'une réaction catalytique. La structure des faces (110) et (111) a d'abord été étudiée en ultra-vide, puis en présence de faibles pressions d'hydrogène et d'oxygène, jusqu'à 10-5 mbar. Le réacteur développé par notre équipe, a ensuite permis d'étudier l'hydrogénation sélective du 1,3-butadiène sur la face (111) sous faisceau X avec pour objectif de caractériser la surface à différents stades de la réaction. Un effet très important de l'hydrogène au niveau volumique ainsi qu'à la surface de l'alliage a été mis en évidence. Ces modifications sont discutées en relation avec les propriétés catalytiques

Spatially resolved, energy-filtered imaging of core level and valence band photoemission of highly p and n doped silicon patterns

International audienceAn accurate description of spatial variations in the energy levels of patterned semiconductor substrates on the micron and sub-micron scale as a function of local doping is an important technological challenge for the microelectronics industry. Spatially resolved surface analysis by photoelectron spectromicroscopy can provide an invaluable contribution thanks to the relatively non-destructive, quantitative analysis. We present results on highly doped n and p type patterns on, respectively, p and n type silicon substrates. Using synchrotron radiation and spherical aberration-corrected energy filtering, we have obtained a spectroscopic image series at the Si 2p core level and across the valence band. Local band alignments doping, band bending and surface photovoltage