No abstract

Silica-, alumina-, and zirconia-supported tantalum oxide and supported vanadia-tantala mixed oxide catalysts were investigated by XRD, UV-vis-DR, FTIR, and FT-Raman spectroscopy to determine the nature of the surface tantala species. Two types of surface TaO x species were identified. On the SiO 2 support, at low coverages tetrahedral TaO 4 species exist, with a TadO bond and three bridging Ta-O-support bonds. At higher coverages, octahedral TaO 6 species occur. On Al 2 O 3 and ZrO 2 both surface species exist already at considerably low Ta loading. The acidic properties of the catalysts were investigated by an FTIR study of adsorbed pyridine. Supported tantala is clearly more Lewis acidic in comparison to vanadia. The oxidation of methanol was used to probe the catalytic performance of the supported oxide species and from the activity and product distribution it is concluded that supported tantala predominantly shows acidic over redox behavior.

The reaction of Fe(acac)3 with the surface of zirconia has been studied for the first time using in situ infrared diffuse reflectance spectroscopy, photoacoustic spectroscopy, and Fourier transform Raman spectroscopy. The unstable Fe(acac)3 reacts readily with the surface of zirconia at room temperature in the liquid phase or at 110 °C in the gas phase, yielding grafted Fe−OH species and Zr−acac surface groups. We present evidence that the reaction occurs both with coordinatively unsaturated Zr sites and with the surface hydroxyls. The grafted Zr−acac groups are thermally unstable and form Zr−acetate groups after thermal treatment at 110 °C in ambient air. After removal of the organic ligands, noncrystalline iron oxide species are formed on the zirconia surface. The grafting of iron oxide on zirconia is a relevant procedure to form either redox catalysts or solid-state fuel cells.

Supported vanadium and titanium oxide catalysts were prepared by adsorption and subsequent calcination of the vanadyl and titanyl acetylacetonate complexes, respectively, on mesoporous SBA-15 by the molecular designed dispersion (MDD) method. Liquid and gas phase depositions at different temperatures were carried out with vanadyl acetylacetonate, and the different results together with those of titanyl acetylacetonate in the liquid phase deposition were discussed. The bonding mechanism, the influence of the metal interaction with the support material, and differences due to the way of deposition and the temperature were investigated by TGA, chemical analysis, FTIR, and Raman spectroscopy. Elevated dissolving temperatures in the liquid phase led to higher final loadings on the SBA-15 without the formation of clusters, even at high loadings. The decomposition of the anchored vanadium and titanium complexes, their thermal stability, and the conversion to the covalently bound VO(x) and TiO(x) species on SBA-15 were studied and investigated by in situ transmission IR spectroscopy. In general, the titanium complex is more reactive than the vanadium complex toward the surface of SBA-15 and has a higher thermal stability. The MDD method of the VO(acac)2 and TiO(acac)2 enables to create a dispersed surface of supported VO(x) and TiO(x), respectively. The structure configurations of VO(x) and TiO(x) oxide catalysts obtained at different metal loadings were studied by Raman spectroscopy. Pore size distributions, XRD, and N2 sorption confirmed the structural stability of these materials after grafting. VO(x)/SBA-15 and TiO(x)/SBA-15 samples, with different metal loadings, were also catalytically tested for the selective catalytic reduction (SCR) of NO with ammonia.