Izabela Genova

Copper-cobalt ferrites as catalysts for methanol decomposition

AbstractCopper-cobalt ferrites with composition Cu1−xCoxFe2O4, where x= 0.2 and 0.8 were prepared by thermal treatment of co-precipitated precursor. The obtained materials were characterized by TG-DSC, XRD, Transmission and Conversion Electron Mössbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic properties of ferrites were tested in methanol decomposition to CO and hydrogen.

Activated carbon from waste biomass as catalyst support: formation of active phase in copper and cobalt catalysts for methanol decomposition

Activated carbons (AC) from various waste agriculture precursors with different texture and surface characteristics were obtained by different preparation procedures. These AC were used as a host matrix of mono- and bi-component copper and cobalt nanoparticles. The effect of carbon properties on the formation of copper/cobalt phases was studied by Boehm method, XRD, nitrogen physisorption, UV–Vis, FTIR, TPR–TG analysis and methanol decomposition as a catalytic test. The elucidation of activated carbons from waste biomass as catalyst support was based on the comparative study with similar materials supported on mesoporous silica KIT-6. It was demonstrated that contrary to KIT-6, the reduction properties of AC support hinders the formation of spinel CuCo2O4 phase in the bi-component materials, but provides formation of mixture of finely dispersed and highly active and selective in methanol decomposition Cu2O and CoO nanoparticles.

Effect of porous structure on the formation of active sites in manganese hosted in ordered mesoporous silica catalysts for environmental protection

Recently ordered mesoporous silicas have been considered as suitable catalyst supports due to their high surface area, well developed porous volume and tuned size, shape and topology of mesopores. Among them SBA-15 and KIT-6 are most promising and studied materials as host matrix of metal/metal oxide nanoparticles. Both structures are characterized with cylindrical mesopores which are 2D- and 3D-packed in the SBA-15 and KIT-6 silicas, respectively. The flexibility of the oxidation state of manganese ensures high oxygen storage capacity of its oxides and provokes their wide application as catalysts in various redox processes. The aim of the current investigation is to clear the effect of pore topology in SBA-15 and KIT-6 mesoporous silicas on the state of the hosted in them manganese oxide nanoparticles. The samples were obtained by incipient wetness impregnation of silicas with manganese nitrate and conventional SiO2 was also used as a reference support. A complex of physicochemical techniques, such as nitrogen physisorption, X-ray diffraction, UV–Vis, XPS, FTIR and temperature-programmed reduction with hydrogen was used for samples characterization. The obtained modifications were tested as potential catalysts for environmental protection via total oxidation of VOCs (ethyl acetate) or hydrogen production from methanol as clean and effective alternative fuel. It was established that the porous structure of mesoporous silica supports influences in a complex way the catalytic behaviour of their manganese modifications, which is determined by the specificity of the reaction medium.

Nanostructured copper, chromium, and tin oxide multicomponent materials as catalysts for methanol decomposition: 11C-radiolabeling study

Copper and chromium modified tin oxide nanocomposites were obtained via incipient wetness impregnation of high surface area nanosized SnO(2) with the corresponding metal acetylacetonates and their further decomposition in air. Powder X-ray diffraction (XRD), Nitrogen physisorption, UV-Vis, and Temperature-programmed reduction (TPR) with hydrogen were applied for the samples characterization. The catalytic activity of the obtained materials was tested in methanol conversion. A new approach based on the selective coverage of the surface with (11)C-methanol was used for the characterization of the catalytic sites. It was demonstrated that the products distribution could be controlled by the surface coverage with methanol and the role of different active sites was discussed. The modification of SnO(2) with copper oxide increased the activity in methanol decomposition to CO(2)via dioxymethylene intermediates, but the catalyst suffered considerable loss of activity due to the reduction transformations by the reaction medium and formation of an inactive intermetallic alloy. The modification with chromium changed the acid-basic properties of SnO(2) by the formation of Cr(2)O(3) nanoparticles as well as anchored to the support chromate species. The former particles facilitated the formation of dimethyl ether (DME), while the latter species converted methanol predominantly to hydrocarbons. The fraction of chromate species increased in Cu-Cr-Sn oxide multicomponent nanocomposites and promoted the formation of hydrocarbons over DME at low temperatures, while at higher temperatures, the activity of the copper species leading to CO(2) formation was more pronounced.

Formation of catalytic active sites in copper and manganese modified SBA-15 mesoporous silica

A series of copper and manganese oxides modified SBA-15 mesoporous silicas with different composition was prepared by incipient wetness impregnation with the corresponding nitrate precursors and compared with the analogous materials supported on conventional SiO2. Nitrogen physisorption, XDR, FTIR, UV–Vis and temperature programmed reduction with hydrogen were used for samples characterization. Their catalytic activity was tested in ethyl acetate oxidation and methanol decomposition. The ordered porous structure of the support facilitates the interaction between different metal oxide nanoparticles and increases their dispersion due to the formation of mixed oxide phase. The ethyl acetate oxidation on SBA-15 binary materials is suppressed due to the lower accessibility of the metal oxide particles, located deeply into the micro-meso pores of the support. The reaction medium which forms during the methanol decomposition provides the reduction/decomposition transformations with the mixed oxide phase. The final phase composition of finely dispersed Cu/CuO and MnOx particles stabilizes in a highly dispersed state into the porous matrix of SBA-15 support and increases the catalytic activity in methanol decomposition due to the appearance of synergistic effect between them.