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Zirconia-ceria solid-solutions are extensively used as promoters for three-way catalysts, in addition, these materials can be used as anodes in solid oxide fuel cells (SOFCs) operated with hydrocarbons. The structural features of ZrO2-CeO2 materials in combination with oxygen storage/release capacity (OSC) are crucial for various catalytic reactions. The direct use of hydrocarbons as fuel for the SOFC (instead of pure H2), without the necessity of reforming and purification reactors can improve global efficiency of the system. The samples preparation method was developed using Zr and Ce chloride precursors, HCl aqueous solution, Pluronic P123, NH4OH and a Teflon autoclave. The samples were dried and calcined, until 540°C. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)×6H2O, calcinated in air until 350°C for 2 hours. In-situ XANES experiments are capable to evaluate the reduction/oxidation potencial of Ni and Ce species in ZrO2-CeO2/Ni samples during partial/total methane oxidation and reduction reactions with H2. The experiments at the Ni K-edge/Ce L3-edge were collected at the LNLS D06A-DXAS beam line in transmission mode, using a Si(111) monochromator and a CCD camera as detector. The data were acquired during a series of temperature programmed reduction steps (TPR), under a 5% H2/He until 600°C, and mixtures of 20%CH4:5%O2/He with 2:1, 1:1 and 1:2 ratios. After each process with CH4 and O2, a TPR procedure was performed in order to evaluate the reduction capacity of the sample after reactions with CH4. The results demonstrated that NiO embedded in the porous ZrO2-CeO2 matrix, reduces at lower temperatures than standard NiO, measured in the same conditions, revealing that the mesoporous support improves the reduction of impregnated NiO. For both edges, there was formation of H2 during partial methane oxidation at 600°C. The total oxidation of methane was observed in lower temperatures (500°C). These results reveal that a high ceria content (90%) could be a great candidate for the SOFC anode.
abstracts
In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of nanostructured La0.6Sr0.4CoO3 (LSCO) and La0.6Sr0.4(Co;Fe)O3 (LSCFO) cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 10000C in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions by X-ray absorption spectroscopies. For this purpose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder diffraction investigations.
abstracts
This work reports preliminary results of the application of a theoretical model [1] in the study of incorporation and release of biological molecules from the porous structure of the SBA-15 [2] ordered mesoporous silica. A theoretical model taking into account the shape and spatial coordination of the pores in the amorphous silica structure is fitted through a non-linear least-squares method and the behavior of the parameters obtained from curves acquired in-situ during incorporation and release experiments are interpreted in the context of different media. Preliminary studies included experiments regarding the coating of the SBA-15 silica with the Eudragit® polymer and the stability of SBA-15 in experimental media (water and PBS solution) and in simulated body fluids. Small angle X-ray scattering experiments were performed mainly with bovine serum albumin (BSA) and insulin, and showed the silica's capacity of sheltering those molecules inside its structure, as well as the influence of Eudragit® on their release dynamics. In-situ experiments made during the incorporation and release of insulin helped elucidate the dynamics of those phenomena, through the reinterpretation of the theoretical model, which was originally designed to study the synthesis process of SBA-15. In this model, fit parameters were monitored during the experiment and, from their behaviors, some conclusions are drawn, such as the delay in BSA release for the SBA-15 plus Eudragit® in gastric fluid. The in-situ studies of insulin loading showed that this molecule's uptake takes place in the course of a few minutes and that it remains inside the pores. Also the in-situ studies of insulin release showed that this molecule is protected inside the silica walls, and the use of Eudragit® is, in a way, optional.
