Aude Bailly

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

A 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 Pd(8)Ni(92)(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.

Looking by grazing incidence small angle x-ray scattering at gold nanoparticles supported on rutile TiO2(110) during CO oxidation

The catalytic activity of oxide-supported gold nanoparticles depends crucially on their size. The present work describes a dedicated set-up in which particle size is determined by grazing incidence small angle x-ray scattering (GISAXS) and reactivity is analysed via a mass spectrometer. Catalytically active gold nanoparticles supported on TiO2(110) of size ranging between 2.4 and 5 nm were characterized during the CO oxidation at pressures in the range 0.1–100 mbar. The growth was found 3D and the particles were best modelled by a truncated sphere. The reaction rate per Au atom measured at 470 K was seen to increase in a monotone manner as the cluster size decreases, without reaching any maximum. Particles of size lower than 3 nm were stable under oxygen but sintering occurs when CO is added at 470K. That dimension coincides with the switch which was previously observed from nucleation-growth, with particles pinned on defects, to coalescence where particles become independent of defects.

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.

Structure, morphology and magnetism of an ultra-thin [NiO/CoO]/PtCo bilayer with perpendicular exchange bias

Electronic and magnetic properties of nanoscale materials are closely related to the atomic arrangement at the interface shared by different chemical elements. A very precise knowledge of the surface/interface structure is then essential to properly interpret the new properties coming out. Of a particular interest is the relationship between structure, morphology and magnetic properties of exchanged-coupled interfaces in ferromagnetic (FM) and antiferromagnetic (AF) materials. The interaction at the AF/FM interface modifies the magnetic switching properties of the FM film, which turn out to be a usefull property on new magnetic devices technology. We present here an investigation of the buried exchange-coupled interface [NiO/CoO]/[PtCo] grown on a Pt(111) single crystal. The magneto-optical Kerr effect reveals a strong coupling at the interface, by an increasing coercivity, and a spin reorientation of the FM film when ordering occurs in the AF layer. The combination of grazing incidence X-ray diffraction, X-ray reflectivity and soft X-ray resonant magnetic scattering yields a comprehensive description of the system.