Multicomponent oxide systems 800-Cu-Mg-Fe-O and 800-Cu-Mg-Fe-O-Ce were tested as catalysts of selective catalytic oxidation of ammonia to dinitrogen (NH3-SCO) process. Materials were obtained by calcination of hydrotalcite-like compounds at temperature 800 °C. Some catalysts were doped with cerium by the wet impregnation method. Not only simple oxides, but also complex spinel-like phases were formed during calcination. The influence of chemical composition, especially the occurrence of spinel phases, copper loading and impregnation by cerium, were investigated. Materials were characterized by several techniques: X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), low-temperature nitrogen adsorption (BET), cyclic voltammetry (CV), temperature programmed reduction (H2-TPR), UV-vis diffuse reflectance spectroscopy and scanning electron microscopy (SEM). Examined oxides were found to be active as catalysts of selective catalytic oxidation of ammonia with high selectivity to N2 at temperatures above 300 °C. Catalysts with low copper amounts (up to 12 wt %) impregnated by Ce were slightly more active at lower temperatures (up to 350 °C) than non-impregnated samples. However, when an optimal amount of copper (12 wt %) was used, the presence of cerium did not affect catalytic properties. Copper overloading caused a rearrangement of present phases accompanied by the steep changes in reducibility, specific surface area, direct band gap, crystallinity, dispersion of CuO active phase and Cu2+ accessibility leading to the decrease in catalytic activity.
Three generations of cobalt porphyrins were synthesized, physicochemically characterized by FTIR and UV/Vis spectroscopy as well as cyclic voltammetry and applied as catalysts in the oxidation of cycloalkanes with atmospheric molecular oxygen under mild conditions. All examined catalysts were active in the tested reaction, and their catalytic activity varied with the nature and number of substituents on the porphyrin ring. Introduction of electron‐withdrawing or electron‐donating substituents at the porphyrin rings increases the activity of metalloporphyrin complexes. It was found, for the first time, that generation II cobalt porphyrins show higher activity in cycloalkane oxidation than cobalt porphyrins of generation III. The lower catalytic activity of generation III cobalt porphyrins can be attributed to the saddle‐shaped deformation of the porphyrin macrocycle. DFT modeling of Co porphyrins and their interactions with molecular oxygen provided explanations for the observed effects. On the basis of prior reports and the obtained results, a reaction mechanism is proposed and discussed.
Diphenyl sulfide was oxidized to sulfoxide and sulfone over V-doped TiO 2 using a 30% solution of H 2 O 2 . The TiO 2 samples with different intended content of vanadium (0.02, 0.05, 0.1 and 0.18 mass%) were prepared by incipient wetness impregnation. Physicochemical properties of the V-doped TiO 2 were characterized by chemical analysis (ICP-OES), X-ray diffraction (XRD/in situ HT-XRD), UV-Vis diffuse reflectance spectrometry (UV-Vis DRS), N 2 -sorption measurements, electron paramagnetic resonance and cyclic voltammetry. Both vanadium oxide loading and calcination temperature influenced the structure of the V-TiO 2 samples. Vanadium species deposited on TiO 2 decreased temperatures required for anatase to rutile phase transformation. The V-TiO 2 samples were found to be efficient catalysts for oxidation of sulfides to sulfones. The sample with the lowest vanadium content (0.02VTiO 2 ) presented among the studied catalysts the best catalytic properties with respect to high conversion of diphenyl sulfide to diphenyl sulfonate. An increase in vanadium loading resulted in decrease in catalytic activity of the samples. Also non-modified TiO 2 presented significantly lower catalytic activity in comparison with 0.02VTiO 2 . This interesting effect was related to the formation of highly dispersed vanadium species catalytically active in Ph 2 S oxidation in the case of the samples with lower V-content. An increase in vanadium loading results in the formation of more aggregated V-species inactive, or less active, in the process of diphenyl sulfide oxidation.
In the presented studies H-Beta zeolite and H-Beta/meso (mesoporous Beta zeolite obtained by mesotemplate-free method) were modified with Fe3, Fe2Cr, FeCr2 and Cr3, triple-metallic aggregates (oligocations) by ion-exchange method (for comparison also modification with Fe isolated cations was done). Successful synthesis of mesoporous Beta zeolite was confirmed by several techniques such as N2-sorption, PXRD, AAS or NH3-TPD. Modified porosity and acidity of Beta zeolite, as well as the used source of metals, influenced the form (coordination and aggregation), content and reducibility of Fe-and Cr-species in the samples (UV-vis-DRS, AAS, H2-TPR). The obtained samples were tested as catalysts in the process of selective catalytic oxidation of ammonia to dinitrogen (NH3-SCO). The highest activity and selectivity
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