Study of interstitial oxygen mobility in RuSr2GdCu2O8 by internal friction

The discovery of the spatial uniform coexistence of superconductivity and ferromagnetism in ruthenocuprates, RuSr2GdCu2O8 (Ru-1212), has spurred an extraordinary development in the study of the competition between magnetism and superconductivity. However, several points of their preparation process and characterization that determine their superconductive behaviour are still obscure. The improvement of sample preparation conditions involves some thermal treatments in inert atmosphere. Anelastic spectroscopy measurements were made using an inverted torsion pendulum, operating with an oscillation frequency of 38 Hz, temperature in the 90 and 310 K range, heating rate of 1 K/min, and vacuum better than 10(-3) Pa. The results show anelastic relaxation peaks at 210 K related to the presence of interstitial oxygen atoms. The peaks decrease significantly with the oxygen loss caused by the heat treatments in vacuum, appearing again after the annealing of the sample in an oxygen atmosphere. These observed peaks are clearly related to the additional oxygen atoms, with activation energy 0.13 and 0.36 eV, and can be explained in terms by diffusional jumps of interstitial oxygen in the RuO2 planes. (C) 2009 Elsevier B.V. All rights reserved.

Oxygen mobility and structural phase transformation in Bi2Sr2CaCu2O8+delta measured by anelastic spectroscopy

One of the most studied ceramic superconductors for application has been, undoubtedly, Bi2Sr2CaCu2O8+delta. Although being a multiphasic material, it has proved to have great advantages compared to other ceramic systems. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature call distinguish among different atomic jumps that occur inside the various phases or at different local ordering. In this paper, mechanical loss spectra of Bi2Sr2CaCu2O8+delta bar shaped samples, made by a conventional method, have been measured between 80 and 600 K, using a torsion pendulum operating in frequencies below 50 Hz, for samples annealed in vacuum up to 600 K. Possible relaxation mechanisms are proposed to explain the origin of the mechanical-loss peaks observed 300 and 500 K. (C) 2004 Elsevier B.V. All rights reserved.

Interstitial oxygen mobility in superconducting samples of Bi2Sr2CaCu2O8+y

Since high-temperature superconductors were discovered, several studies have been made on their physical properties, attempting to associate them to the origin of superconductivity. Obviously, the oxygen atoms interstitially dissolved in the matrix have an important role in superconductivity, since they move easily in the lattice. In addition, they contribute to hole creation in the CuO2 planes. Anelastic spectroscopy ( internal friction) measurements are sensitive tools for the study of defects in solids, in particular for oxygen mobility. In this paper, Bi2Sr2CaCu2O8+y samples with several different amounts of interstitial oxygen were analysed by means of anelastic spectroscopy measurements. The measurements were performed by using a torsion pendulum operating at a frequency of about 40 Hz. Complex relaxation structures were observed and attributed to the shift of the oxygen interstitial atoms in BiO chains.

Oxygen mobility in SmBa2Cu3O7-delta measured by anelastic spectroscopy

Anelastic spectroscopy has been performed on a sample of superconducting oxide SmBa2Cu3O7-delta (SBCO) using a torsion pendulum operating with frequency around 10 Hz. A thermally activated relaxation peak is observed near 500 K with the activation enthalpy of 1.55 +/- 0.03 eV and the pre-exponential factor of approximately 10(-15) s, which is attributed to the mobility of non-stoichiometric oxygen by jumps in positions O1 and O5 of the lattice. (c) 2006 Elsevier B.V. All rights reserved.

Oxygen mobility in Bi:Sr:Ca:Cu:O ceramic measured using anelastic relaxation methods

Since the discovery of YBaCuO, experiments have shown that its superconducting properties are strongly affected by the oxygen content. More recently, anelastic relaxation measurements in La2CuO4+δ, showed that the decrease in the oxygen content can be related to two events. One is the decrease in mobility between two adjacent CuO planes, and the other is the increase in the number of tilting patterns of the CuO6 octahedra. In the case of the bismuth-based ceramic, it is known that the oxygen content, within some limits, does not affect its superconducting properties. In order to evaluate the mobility and the effect of the oxygen content on this material we have prepared BSCCO ceramic and tested regarding its internal friction and electrical resistivity as a function of the temperature while the oxygen content was being reduced by a sequence of vacuum annelaing at 620 K. The samples were prepared in the Bi:Sr:Ca:Cu = 2212 and 2223 proportion, using powder obtained by the sol-gel route and conventional solid state reaction. The anelastic relaxation measurements were performed using a torsion pendulum operating with frequency about 15-35 Hz between 77 to 700 K. The diffraction pattern of the as sintered and the vacuum annealed material were also presented. The results have shown complex anelastic relaxation structures that were associated to the jump of interstitial oxygen atoms between two adjacent CuO planes. The vacuum annealing showed to be deleterious to the critical temperature of the superconducting ceramic.

Self-cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Nickel catalysts supported on ZrO2, Y2O3-stabilized ZrO2 and CaO-stabilized ZrO2 for the steam reforming of ethanol: Effect of the support and nickel load

Catalysts with various nickel loads were prepared on supports of ZrO2, ZrO2-Y2O3 and ZrO2-CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO2 and cubic phases in the ZrO2-Y2O3 and ZrO2-CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H-2 yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO2 was modified with Y2O3 and CaO, there were big changes in the CO and CO2 concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions. (c) 2007 Published by Elsevier B.V.

Anelastic spectroscopy in SmBa2Cu3O7

The possibility of variable stoichiometry and the high mobility of oxygen in the CuOx planes of SmBa2Cu3O7 give rise to a rich phase diagram. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature can distinguish among the different atomic jumps, which occur in the various phases or at different local ordering. In this paper, it is reported anelastic relaxation measurements in SmBa2Cu3O7, above room temperature, using a torsion pendulum operating in frequencies around 40 Hz. The mobility of oxygen atoms in the CuOx planes in the various phases has been discussed and the thermally activated peak of elastic energy dissipation observed around 500 K was interpreted in that framework. (C) 2004 Elsevier B.V. All rights reserved.

Anelastic characterization and superconducting properties of RuSr2GdCu2O8+delta

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Anelastic spectroscopy in superconducting oxides

Since the discovery of the high Tc superconductors, several works have been made about the different properties of these materials. Anelastic spectroscopy experiments are sensitive tools to the study of defects in solids and phase transitions. By this technique, we can distinguish the different types of atomic jumps that happen to different temperatures. The intensity of the peaks in the anelastic spectrum and the step in the torsional modulus are related with the concentration of the relaxing entities, and the position of the peaks is determined by its mobility. In this paper, the study on Bi and Sm based superconducting oxides was made by anelastic relaxation measurements using a torsion pendulum. The samples were submitted to successive thermal treatments in high vacuum, in the temperature range between 100 K and 650 K, heating rate about 1 K/min. For Bi based superconducting oxides the results shown two peaks, that were associated to interstitial oxygen mobility and to orthorhombic to monoclinic phase transition. For Sm based superconducting oxides the results shown a relaxation peak that was attributed to the jumps of the oxygen atoms in the inter-chains O1 and 05 of the lattice.

Anelastic characterization and superconducting properties of RuSr2GdCu2O8+δ

Since the discovery of the high Tc superconductors, many researches have been carried out on the different properties of these materials, especially on the transition temperature into the superconducting state. The rutheno-cuprates belong to a new class of composites, which were synthesized for the first time by Bauernfeind in 1995. Bernhard and collaborators discovered, in 1999, the coexistence of the ferromagnetism and the superconductivity in this phase, which is known as antagonistic phenomenon in the electromagnetism due to spin-charge interactions established in these states. However, the physical nature of the superconducting and magnetic states is still very obscure. The non-stoichiometric (interstitial) oxygen is considered as a possible cause for the non-uniformity of the sample properties. In this paper, results of mechanical spectroscopy in Ru-1212 samples are presented showing complex anelastic spectra, which were attributed to the mobility of the interstitial oxygen atoms in the Ru-1212 lattice.

Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion

The effect of amorphous (am-), monoclinic (m-), and tetragonal (t-) ZrO2 phase on the physicochemical and catalytic properties of supported Cu catalysts for ethanol conversion was studied. The electronic parameters of Cu/ZrO2 were determined by in situ XAS, and the surface properties of Cu/ZrO2 were defined by XPS and DRIFTS of CO-adsorbed. The results demonstrated that the kind of ZrO2 phase plays a key role in the determination of structure and catalytic properties of Cu/ZrO 2 catalysts predetermined by the interface at Cu/ZrO2. The electron transfer between support and Cu surface, caused by the oxygen vacancies at m-ZrO2 and am-ZrO2, is responsible for the active sites for acetaldehyde and ethyl acetate formation. The highest selectivity to ethyl acetate for Cu/m-ZrO2 catalyst up to 513 K was caused by the optimal ratio of Cu0/Cu+ species and the high density of basic sites (O2-) associated with the oxygen mobility from the bulk m-ZrO2. © 2013 Elsevier Inc. All rights reserved.

Mobilidade de oxigênio intersticial em SM'BA IND.2' C IND.U 'IND.3' 'O IND. 7-'delta' medida através de espectroscopia mecânica

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Cluster-derived Gold/Iron catalysts for environmental applications

During the last years we assisted to an exponential growth of scientific discoveries for catalysis by gold and many applications have been found for Au-based catalysts. In the literature there are several studies concerning the use of gold-based catalysts for environmental applications and good results are reported for the catalytic combustion of different volatile organic compounds (VOCs). Recently it has also been established that gold-based catalysts are potentially capable of being effectively employed in fuel cells in order to remove CO traces by preferential CO oxidation in H2-rich streams. Bi-metallic catalysts have attracted increasing attention because of their markedly different properties from either of the costituent metals, and above all their enhanced catalytic activity, selectivity and stability. In the literature there are several studies demostrating the beneficial effect due to the addition of an iron component to gold supported catalysts in terms of enhanced activity, selectivity, resistence to deactivation and prolonged lifetime of the catalyst. In this work we tried to develop a methodology for the preparation of iron stabilized gold nanoparticles with controlled size and composition, particularly in terms of obtaining an intimate contact between different phases, since it is well known that the catalytic behaviour of multi-component supported catalysts is strongly influenced by the size of the metal particles and by their reciprocal interaction. Ligand stabilized metal clusters, with nanometric dimensions, are possible precursors for the preparation of catalytically active nanoparticles with controlled dimensions and compositions. Among these, metal carbonyl clusters are quite attractive, since they can be prepared with several different sizes and compositions and, moreover, they are decomposed under very mild conditions. A novel preparation method was developed during this thesis for the preparation of iron and gold/iron supported catalysts using bi-metallic carbonyl clusters as precursors of highly dispersed nanoparticles over TiO2 and CeO2, which are widely considered two of the most suitable supports for gold nanoparticles. Au/FeOx catalysts were prepared by employing the bi-metallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO)16] (Fe/Au=1) and [NEt4][AuFe4(CO)16] (Fe/Au=4), and for comparison FeOx samples were prepared by employing the homometallic [NEt4][HFe3(CO)11] cluster. These clusters were prepared by Prof. Longoni research group (Department of Physical and Inorganic Chemistry- University of Bologna). Particular attention was dedicated to the optimization of a suitable thermal treatment in order to achieve, apart from a good Au and Fe metal dispersion, also the formation of appropriate species with good catalytic properties. A deep IR study was carried out in order to understand the physical interaction between clusters and different supports and detect the occurrence of chemical reactions between them at any stage of the preparation. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS was performed in order to investigate the catalysts properties, whit particular attention to the interaction between Au and Fe and its influence on the catalytic activity. This novel preparation method resulted in small gold metallic nanoparticles surrounded by highly dispersed iron oxide species, essentially in an amorphous phase, on both TiO2 and CeO2. The results presented in this thesis confirmed that FeOx species can stabilize small Au particles, since keeping costant the gold content but introducing a higher iron amount a higher metal dispersion was achieved. Partial encapsulation of gold atoms by iron species was observed since the Au/Fe surface ratio was found much lower than bulk ratio and a strong interaction between gold and oxide species, both of iron oxide and supports, was achieved. The prepared catalysts were tested in the total oxidation of VOCs, using toluene and methanol as probe molecules for aromatics and alchols, respectively, and in the PROX reaction. Different performances were observed on titania and ceria catalysts, on both toluene and methanol combustion. Toluene combustion on titania catalyst was found to be enhanced increasing iron loading while a moderate effect on FeOx-Ti activity was achieved by Au addition. In this case toluene combustion was improved due to a higher oxygen mobility depending on enhanced oxygen activation by FeOx and Au/FeOx dispersed on titania. On the contrary ceria activity was strongly decreased in the presence of FeOx, while the introduction of gold was found to moderate the detrimental effect of iron species. In fact, excellent ceria performances are due to its ability to adsorb toluene and O2. Since toluene activation is the determining factor for its oxidation, the partial coverage of ceria sites, responsible of toluene adsorption, by FeOx species finely dispersed on the surface resulted in worse efficiency in toluene combustion. Better results were obtained for both ceria and titania catalysts on methanol total oxidation. In this case, the performances achieved on differently supported catalysts indicate that the oxygen mobility is the determining factor in this reaction. The introduction of gold on both TiO2 and CeO2 catalysts, lead to a higher oxygen mobility due to the weakening of both Fe-O and Ce-O bonds and consequently to enhanced methanol combustion. The catalytic activity was found to strongly depend on oxygen mobility and followed the same trend observed for catalysts reducibility. Regarding CO PROX reaction, it was observed that Au/FeOx titania catalysts are less active than ceria ones, due to the lower reducibility of titania compared to ceria. In fact the availability of lattice oxygen involved in PROX reaction is much higher in the latter catalysts. However, the CO PROX performances observed for ceria catalysts are not really high compared to data reported in literature, probably due to the very low Au/Fe surface ratio achieved with this preparation method. CO preferential oxidation was found to strongly depend on Au particle size but also on surface oxygen reducibility, depending on the different oxide species which can be formed using different thermal treatment conditions or varying the iron loading over the support.

Catalysts and processes for next-generation H2 production

The present study is focused on the development of new VIII group metal on CeO2 – ZrO2 (CZO) catalyst to be used in reforming reaction for syngas production. The catalyst are tested in the oxyreforming process, extensively studied by Barbera [44] in a new multistep process configuration, with intermediate H2 membrane separation, that can be carried out at lower temperature (750°C) with respect the reforming processes (900 – 1000°C). In spite of the milder temperatures, the oxy-reforming conditions (S/C = 0.7; O2/C = 0.21) remain critical regarding the deactivation problems mainly deriving from thermal sintering and carbon formation phenomena. The combination of the high thermal stability characterizing the ZrO2, with the CeO2 redox properties, allows the formation of stable mixed oxide system with high oxygen mobility. This feature can be exploited in order to contrast the carbon deposition on the active metal surface through the oxidation of the carbon by means of the mobile oxygen atoms available at the surface of the CZO support. Ce0.5Zr0.5O2 is the phase claimed to have the highest oxygen mobility but its formation is difficult through classical synthesis (co-precipitation), hence a water-in-oil microemulsion method is, widely studied and characterized. Two methods (IWI and bulk) for the insertion of the active metal (Rh, Ru, Ni) are followed and their effects, mainly related to the metal stability and dispersion on the support, are discussed, correlating the characterization with the catalytic activity. Different parameters (calcination and reduction temperatures) are tuned to obtain the best catalytic system both in terms of activity and stability. Interesting results are obtained with impregnated and bulk catalysts, the latter representing a new class of catalysts. The best catalysts are also tested in a low temperature (350 – 500°C) steam reforming process and preliminary tests with H2 membrane separation have been also carried out.