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Abstract: Understanding the metal–support interaction (MSI) is crucial to comprehend how the catalyst support affects performance and whether this interaction can be exploited in order to design new catalysts with enhanced properties. Spatially resolved soft X-ray absorption spectroscopy (XAS) in combination with Atomic Force Microscopy (AFM) and Scanning Helium Ion-Milling Microscopy (SHIM) has been applied to visualise and characterise the behaviour of individual cobalt nanoparticles (CoNPs) supported on two-dimensional substrates (SiOxSi(100) (x < 2) and rutile TiO2(110)) after undergoing reduction–oxidation–reduction (ROR). The behaviour of the Co species is observed to be strongly dependent on the type of support. For SiOxSi a weaker MSI between Co and the support allows a complete reduction of CoNPs although they migrate and agglomerate. In contrast, a stronger MSI of CoNPs on TiO2 leads to only a partial reduction under H2 at 773 K (as observed from Co L3-edge XAS data) due to enhanced TiO2 binding of surface-exposed cobalt. SHIM data revealed that the interaction of the CoNPs is so strong on TiO2, that they are seen to spread at and below the surface and even to migrate up to ∼40 nm away. These results allow us to better understand deactivation phenomena and additionally demonstrate a new understanding concerning the nature of the MSI for Co/TiO2 and suggest that there is scope for careful control of the post-synthetic thermal treatment for the tuning of this interaction and ultimately the catalytic performance.

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Abstract: We report the evolution of metastable precursor structures during hydrogen infusion in the near-surface region of a super duplex stainless steel. Grazing-incidence x-ray diffraction was employed to monitor, operando, the lattice degradation of the austenite and ferrite phases. Electrochemical hydrogen charging resulted in the splitting of the diffraction peaks of the austenite phase, suggesting the evolution of a metastable precursor structure. This may be explained by the formation of quasi-hydrides, which convert back into the austenite parent structure during hydrogen effusion. The ferrite showed less lattice deformation than the austenite and no phase transformation.

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Abstract: NixFe3−x Ni x Fe 3 − x O4 thin films with varying Ni amount (0 ≤ ≤ x ≤ ≤ 1.5) were deposited on MgO(001) via reactive molecular beam epitaxy. The growth process was monitored during film deposition by means of X-ray diffraction. All prepared films exhibit a well-ordered structure with complete vertical crystallinity throughout the whole film growth and flat surfaces of the final films independent of the Ni amount. An enhancement of the vertical compression in the initial growth continuously decreases up to a film thickness of 8 nm. During further growth, all films exhibit residual and constant vertical compression with lateral adaption of the final films to the substrate lattice, as observed by high energy surface X-ray diffraction experiments. Hard X-ray photoelectron spectroscopy measurements of the final films reveal increasing Fe3+ Fe 3 + :Fe2+ Fe 2 + ratios for higher Ni content and point to additional NiO agglomerations within the films exceeding the stoichiometric Ni amount of x = 1.

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Abstract: Adsorption and incorporation of ions is known to influence the morphology and growth of calcite. Using surface X-ray diffraction, the interfacial structure of calcite in contact with CaCO3, MgCl2, CaCl2 and BaCl2 solutions was determined. All of these conditions yield a comparable interfacial structure, meaning that there is no significant ion adsorption on the terraces under the investigated conditions. This allows for the first time a thorough comparison in all three dimensions with state-of-the-art computer simulations, involving molecular dynamics based on both DFT and two different force field models. Additionally, the simulated structures are used to calculate the corresponding structure factors, which in turn are compared to those obtained from experiment, thereby avoiding the need for fitting or subjective interpretation. In general, there is a good agreement between experiment and the simulations, though there are some small discrepancies in the atomic positions, which lead to an inadequate fit of certain features characteristic of the structure of water at the interface. Of the three simulation methods examined, the DFT results were found to agree best with the experimental structure.

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Abstract: The real-time morphological evolution of vacuum deposited α-sexithiophene (α-6T) on a weakly interacting (glass) substrate at ambient temperature is reported. In-situ grazing incidence small angle X-ray scattering (GISAXS) enabled the observation of nanoscale aggregates while in-situ grazing incidence wide angle scattering (GIWAXS) allowed the study of the molecular-scale morphology. The in-situ GISAXS measurements revealed that the α-6T growth proceeds via a Stranski-Krastanov mode, whereby 2-4 complete monolayers are deposited followed by subsequent layers formed via island growth. In-situ GIWAXS also showed the evolution of the polymorph composition during the thin film growth. Initially the disordered β-phase and the low-temperature (LT) phase are deposited in nearly equal proportion until a thickness of 8 nm whereby the LT-phase begins to dominate until a final α-6T thickness of 50 nm where the scattering intensity of the LT-phase is more than double that of the β-phase. The change in polymorph composition coincided with an increase in the LT-phase d-spacing, indicating a lattice strain relief as the thin film moves from surface to bulk mediated growth. The GISAXS findings were confirmed through direct imaging using ex-situ atomic force microscopy (AFM) at various thicknesses revealing the existence of both initial monolayers and intermediate and final island morphologies. The findings reveal the real-time morphological evolution of α-6T across both the molecular scale and the nanoscale and highlight the role of strain in polymorph growth. Due to the importance of thin film microstructure in device performance, it is expected that these results will aid in the development of the structure-property relationships necessary to realise the full potential of organic electronics.