Browsing by Subject "Thermally induced"

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    Direct evidence for the instability and deactivation of mixed-oxide systems: influence of surface segregation and subsurface diffusion
    (2011) Emmez, E.; Vovk, E. I.; Bukhtiyarov V. I.; Ozensoy, E.
    In the current contribution, we provide a direct demonstration of the thermally induced surface structural transformations of an alkaline-earth oxide/transition metal oxide interface that is detrimental to the essential catalytic functionality of such mixed-oxide systems toward particular reactants. The BaOx/TiO2/Pt(111) surface was chosen as a model interfacial system where the enrichment of the surface elemental composition with Ti atoms and the facile diffusion of Ba atoms into the underlying TiO2 matrix within 523 873 K leads to the formation of perovskite type surface species (BaTiO3/Ba2TiO4/BaxTiyOz). At elevated temperatures (T > 973 K), excessive surface segregation of Ti atoms results in an exclusively TiO2/TiOx-terminated surface which is almost free of Ba species. Although the freshly prepared BaOx/TiO2/Pt(111) surface can strongly adsorb ubiquitous catalytic adsorbates such as NO2 and CO2, a thermally deactivated surface at T > 973 K practically loses all of its NO2/CO2 adsorption capacity due to the deficiency of surface BaOx domains.
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    Nature of the Ti-Ba interactions on the BaO/TiO2/Al 2O3 NOx storage system
    (2009) Andonova, S. M.; Şentürk, G. S.; Kayhan, E.; Ozensoy, E.
    A ternary oxide-based NO* storage material in the form of BaOZTiO2Zy-Al2O3 was synthesized and characterized. Thermally induced structural changes occurring on the surfaces of the TiO2Zy-Al2O3 and BaOZ TiO 2Zy-Al2O3 systems were studied in a comparative manner within 300-1273 K via X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and BET surface area analysis. The surface acidity of the studied oxide systems was also investigated via pyridine adsorption monitored by in-situ Fourier transform infrared (FTIR) spectroscopy. BaO/TiO2γ-Al 2O3 ternary oxide was synthesized by incorporating different loadings of (8-20 wt %) BaO onto the TiO2/γ Al 2O3 support material, which was originally prepared using the sol-gel method. In the TiO2Zy-Al2O3 binary oxide support material, anatase phase exhibited a relatively high thermal stability at T < 1073 K. The presence of TiO2 domains on the surface of the alumina particles was found to alter the surface acidity of alumina by providing new medium-strength Lewis acid sites. SEMZEDX results indicate that in the BaO/TiO2γ-Al2O3 system, TiO2 domains present a significant affinity toward BaO and/or Ba(NO3) 2 resulting in a strong Ti-Ba interaction and the formation of overlapping domains on the surface. The presence of TiO2 also leads to a decrease in the decomposition temperature of the Ba(N03) 2 phase with respect to the Ti-free Ba(N03) 2ZyAl2O3 system. Such a destabilization is likely to occur due to a weaker interaction between Ba(N03) 2 and y-Al203 domains in the ternary oxide as well as due to the change in the surface acidity in the presence of TiO 2. At relatively high temperatures (e.g., 873-1273 K) formation of complex structures in the form of BaTiO3, Ba1.23Al 2.46Ti5.54O16, BaTiO5, andor Ba x:AlyTizOn., were also observed. © 2009 American Chemical Society.