209 research outputs found
Influence of calcination conditions on structural and solid‐state kinetic properties of iron oxidic species supported on SBA‐15
Iron oxidic species supported on silica SBA-15 were synthesized with various iron loadings using two different FeIII precursors. The effect of varying powder layer thickness during calcination on structural and solid-state kinetic properties of FexOy/SBA-15 samples was investigated. Calcination was conducted in thin (0.3 cm) or thick (1.3 cm) powder layer. Structural characterization of resulting FexOy/SBA-15 samples was performed by nitrogen physisorption, X-ray diffraction, and DR-UV/Vis spectroscopy. Thick powder layer during calcination induced an increased species size independent of the precursor. However, a significantly more pronounced influence of calcination mode on species size was observed for the FeIII nitrate precursor compared to the FeIII citrate precursor. Temperature-programmed reduction (TPR) experiments revealed distinct differences in reducibility and reduction mechanism dependent on calcination mode. Thick layer calcination of the samples obtained from FeIII nitrate precursor resulted in more pronounced changes in TPR profiles compared to samples obtained from FeIII citrate precursor. TPR traces were analyzed by model-dependent Coats-Redfern method and model-independent Kissinger method. Differences in solid-state kinetic properties of FexOy/SBA-15 samples dependent on powder layer thickness during calcination correlated with differences in iron oxidic species size.TU Berlin, Open-Access-Mittel - 201
Influence of Adding Molybdenum on Structure and Performance of FexOy/SBA‐15 Catalysts in Selective Oxidation of Propene
Mixed iron and molybdenum oxide catalysts supported on nanostructured silica, SBA‐15, were synthesized with various Mo/Fe atomic ratios ranging from 0.07/1.0 to 0.57/1.0. Structural characterization of as‐prepared MoxOy_FexOy/SBA‐15 samples was performed by nitrogen physisorption, X‐ray diffraction, and DR‐UV‐Vis spectroscopy. Adding molybdenum resulted in a pronounced dispersion effect on supported iron oxidic species. Increasing atomic ratio up to 0.21Mo/1.0Fe was accompanied by decreasing species sizes. Strong interactions between iron and molybdenum during the synthesis resulted in the formation of Fe−O−Mo structure units, possibly Fe2(MoO4)3‐like species. Reducibility of MoxOy_FexOy/SBA‐15 catalysts was investigated by temperature‐programmed reduction experiments with hydrogen as reducing agent. The lower reducibility obtained when adding molybdenum was ascribed to both dispersion and electronic effect of molybdenum. Catalytic performance of MoxOy_FexOy/SBA‐15 samples was studied in selective gas‐phase oxidation of propene with O2 as oxidant. Adding molybdenum resulted in an increased acrolein selectivity and a decreased selectivity towards total oxidation products.TU Berlin, Open-Access-Mittel - 201
Synthesis, Characterization, and Catalytic Activity of Zirconium Oxide Nitrides Supported on High-surface SiO2
Zirconium oxide nitrides are active ammonia decomposition catalysts for the production of hydrogen. We present a route to zirconium oxide nitrides with high surface area. The precursor used consisted of a high-surface-area silica material coated with zirconium alkoxide. Subsequent hydrolysis and calcination resulted in ZrO2 supported on SiO2. The high surface area of the material could be maintained in the following ammonolysis procedure leading to the corresponding zirconium oxide nitride. In contrast to the as-prepared ZrO2, the zirconium oxide nitrides exhibited a significant catalytic activity in ammonia decomposition, but compared to an iron oxide-based reference material, the new oxide nitrides showed a rather low activity. Nevertheless, zirconium oxide nitrides constitute suitable model systems for elucidating the effect of nitrogen in the anion substructure on the activity and selectivity of oxide-based ammonia decomposition catalysts
Catalytic Methanol Oxidation over Copper: Observation of Reaction-Induced Nanoscale Restructuring by Means of In Situ Time-Resolved X-ray Absorption Spectroscopy
Розповсюдження та збут фальсифікованих засобів захисту рослин, як від порушення прав інтелектуальної власності: проблеми суспільної безпеки
Synthesis and characterization of metastable transition metal oxides and oxide nitrides
New routes to vanadium sesquioxide and tantalum oxide nitride (γ- and δ-phase) are presented. Phase pure V2O3 with bixbyite-type structure, a metastable polymorph, was obtained from vanadium fluoride hydrates at ~750 K. It crystallizes in the cubic crystal system in space group Ia3¯ with lattice parameter a=939.30(5) pm. The catalytical properties of the corresponding oxide nitride phases and their oxidation and reduction solid-state kinetics were investigated. The preparation of γ-TaON as a phase pure sample can be realized by ammonolysis of X-ray amorphous tantalum oxide precursors at 1073 K. This metastable tantalum oxide nitride crystallizes in the monoclinic VO2(B)-type structure in space group C2/m. The same precursors can be used to synthesize the δ-modification with an anatase-type structure at 1023 K. It crystallizes in the tetragonal crystal system in space group I41/amd. A maximum yield of 82 m % could be obtained. The fundamental band gaps of the synthesized and of other metastable TaON polymorphs were calculated from first principles using the GW method. The present results are compared to experimental data and to previous calculations at hybrid DFT level
Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy
The local structure of vanadium oxide supported on nanostructured SiO2 (VxOy/SBA-15) was investigated by in situ X-ray absorption spectroscopy (XAS). Because the number of potential parameters in XAS data analysis often exceeds the number of "independent" parameters, evaluating the reliability and significance of a particular fitting procedure is mandatory. The number of independent parameters (Nyquist) may not be sufficient. Hence, in addition to the number of independent parameters, a novel approach to evaluate the significance of structural fitting parameters in XAS data analysis is introduced. Three samples with different V loadings (i.e. 2.7 wt %, 5.4 wt %, and 10.8 wt %) were employed. Thermal treatment in air at 623 K resulted in characteristic structural changes of the V oxide species. Independent of the V loading, the local structure around V centers in dehydrated VxOy/SBA-15 corresponded to an ordered arrangement of adjacent V2O7 units. Moreover, the V2O7 units were found to persist under selective oxidation reaction conditions
The modification of MoO3 nanoparticles supported on mesoporous SBA-15: characterization using X-ray scattering, N2 physisorption, transmission electron microscopy, high-angle annular darkfield technique, Raman and XAFS spectroscopy
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