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Effect of fluorite-like or perovskite-like complex oxide promoters and Pd on the performance of Ni/YSZ and Ni/ScSZ cermets in methane steam reforming or selective oxidation by O2 into syngas at short contact times was studied. Spatial uniformity of dopants distribution in composites was controlled by TEM combined with EDX, while the lattice oxygen mobility and reactivity was elucidated by CH4 and H2 TPR. Oxide promoters allow to operate even at stoichiometric H2O/CH4 ratio by suppressing coke deposition through modification of Ni surface, while doping by Pd ensures reasonable performance at moderate (∼550 °C) temperatures required for Intermediate–Temperature Solid Oxide Fuel Cells (IT SOFC).
Some perovskite –like Fe (Co) -containing and fluorite-like Bi –containing solid solutions considered as promising materials for high oxygen flux membranes application have been synthesized by the mechanochemical activation route. Structural/microstructural features of those systems characterized by TEM, XRD, IR, and Raman spectroscopy are compared with the data on their mixed conductivity and oxygen mobility. Some properties of nanocomposites comprised of those materials and such oxides as Fe2O3, BaTiO3, BaBiO3 etc are elucidated as well. Densification of those powdered samples by sintering in the 700–1400 K temperature range is accompanied by annealing of metastable phases generating “core-shell” nanocomposites with oxygen transport properties different from those of traditional materials.
Ca and/or F-modified samples of LaMnO3 have been prepared by the Pechini method. The bulk structure of samples was characterized by TEM, EXAFS and XRD, while the surface composition was studied by SIMS. Thermal analysis, O2 TPD, H2 TPR and isothermal pulse/flow samples reduction by CO were applied to characterize the accessible surface/bulk oxygen mobility and reactivity. A reasonable description of the experimental energetic spectrum of the surface oxygen for various types of regular and defect surface sites on the perovskite faces was achieved by using semiempirical Interacting Bonds Method in the slab approximation with a due regard for the surface face termination and relaxation. Fluorine was found to decrease the surface coverage by reactive weakly bound oxygen forms while increasing the bulk oxygen excess and mobility. Calcium generated reactive weakly bound oxygen forms while decreasing the oxygen excess in the lattice and converting the regular M-O oxygen forms into the bridging ones through migration to the surface.
This work presents results of investigation of the charge and coordination state of Fe cations in La1-xMexFeO3-y perovskites prepared by mechanochemical route by using MÖssbauer spectroscopy as related to bulk oxygen reactivity in H2 or in CH4 temperature-programmed reduction (TPR).
La0.8Sr0.2Fe0.6Ni0.4O2.9 (LSFN) and LSFN-La9.83Si4.5Fe1.5O26 (LSiF) nanocomposite were synthesized and investigated as cathode materials for intermediate temperature (IT) solid oxide fuel cells (SOFC). Phase and structure evolution with sample sintering temperature as well as their transport properties and catalytic activity in oxygen reduction were studied.
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