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Particle sintering and reshaping constitute the main cause for catalyst deactivation. An atomic-scale understanding of the correlation among the catalyst structure, its support, and the gas phase under realistic reaction conditions is required for its suppression. In this study, we combined high-energy grazing incidence X-ray diffraction, in situ mass spectrometry, ex situ scanning electron microscopy, and density functional theory calculations to unravel the driving force behind the composition-dependent particle shape changes and sintering processes of alpha-Al2O3(0001)-supported Pt-Pd alloy nanoparticles under realistic reaction conditions for CO oxidation. We find that pure Pt and Pt-rich particles, initially kinetically trapped in metastable flat particle shapes, undergo a strong reaction-induced height increase to adopt a more stable, theoretically predicted compact equilibrium shape. Contrarily, Pd-rich particles prove to be more resistant against shape changes, since they exhibit already a shape close to equilibrium. We thus conclude that the observed initial deviations in particle shape from the theoretical predictions are due to kinetic limitations during growth. Our data provide information on the segregation state of the alloy particles, indicating a Pt core and Pd shell structure under strongly reducing conditions and the alloying of Pt and Pd under the reaction conditions for CO oxidation close to stoichiometry.

Structural insight into nano-objects down to the atomic scale is one of the most important prerequisites in understanding functional materials properties and will ultimately permit to relate the size and shape of nanoparticles to their catalytic activity. We elucidate the potential of extracting structural information about a small ensemble of nanoparticles semi-regularly arranged on a periodic array from coherent X-ray Bragg diffraction. The observed superstructure in the Pt(111) Bragg peak obviously originates from the mutual interference of the Bragg scattered wave field from individual nanoparticles in the nano-array. Despite the absence of a symmetry center in the Bragg peak of the nano-array, we identify the most prominent in-plane spatial frequencies of the latter by applying a Patterson map analysis to the Bragg peak superstructure. Integration along the out-of-plane reciprocal space direction over the relevant in-plane regions of interest results in Laue oscillations that arise from nanoparticle sets of similar heights in real space. A one-to-one comparison with real-space microscopic information obtained from SEM and AFM suggests potential nanoparticle subsets as origin for the X-ray intensity in these regions of interest by the good agreement in their height and direction-dependent in-plane interparticle distances, as also further supported by simulations. Nanoparticle arrays with well-defined tunable sizes and lateral distances may serve in the future to track structural changes of smallest catalysis-relevant nanoparticles during operando heterogeneous catalysis experiments in the 10 nm size regime.

Different SrTiO3 thin films are investigated to unravel the nature of ultra-low conductivities recently found in SrTiO3 films prepared by pulsed laser deposition. Impedance spectroscopy reveals electronically pseudo-intrinsic conductivities for a broad range of different dopants (Fe, Al, Ni) and partly high dopant concentrations up to several percent. Using inductively-coupled plasma optical emission spectroscopy and reciprocal space mapping, a severe Sr deficiency is found and positron annihilation lifetime spectroscopy revealed Sr vacancies as predominant point defects. From synchrotron-based X-ray standing wave and X-ray absorption spectroscopy measurements, a change in site occupation is deduced for Fe-doped SrTiO3 films, accompanied by a change in the dopant type. Based on these experiments, a model is deduced, which explains the almost ubiquitous pseudo-intrinsic conductivity of these films. Sr deficiency is suggested as key driver by introducing Sr vacancies and causing site changes (FeSr and TiSr) to accommodate nonstoichiometry. Sr vacancies act as mid-gap acceptor states, pinning the Fermi level, provided that additional donor states (most probably Ti_Sr) are present. Defect chemical modeling revealed that such a Fermi level pinning also causes a self-limitation of the Ti site change and leads to a very robust pseudo-intrinsic situation, irrespective of Sr/Ti ratios and doping.

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RU Radboud Universiteit, 29 september 2016, Promotor : Vlieg, Elias Co-promotores : Vonk, V., honkim"aki, V., Contains fulltext : 158976.pdf (publisher's version ) (Open Access)

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X-ray Diffraction (XRD) is an outstanding tool for structural analyses at the atomic scale, and both the experimental techniques and the theoretical interpretations are well established. X-rays also have the advantage of being highly penetrating, as compared to electrons for instance, allowing for the study of bulk materials, or to study samples in complicated environments. The high photon fluxes available at third generation synchrotron sources make it possible to collect full diffraction patterns in relatively short times, and thus to follow time varying processes in-situ. In the frst part of this chapter we briefly discuss the advantages and disadvantages of X-rays as compared to other probes like electrons or neutrons. In the second part as an example in-situ surface X-ray diffraction studies of growing films using pulsed laser deposition (PLD) will be presented. The hetero-epitaxial growth process, especially of the first mono-layers can only be understood by in-situ diffraction studies in the PLD chamber under deposition conditions. Also high energy diffraction of buried interfaces will be discussed briefly. The final part of this chapter will present the possibilities for in-situ diffraction studies at the upcoming Free-Electron Laser sources, with fully coherent beams and sufficient intensities to collect full diffraction patterns with single 100 femto-second pulses. The characteristics of the Free-Electron-Lasers and various planned experiments will be presented. © Springer-Verlag Berlin Heidelberg 2014., Language of Original Document: English

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