Improvement in the Reduction Behavior of Novel ZrO(2)-CeO(2) Solid Solutions with a Tubular Nanostructure by Incorporation of Pd

In this work, 1 wt % Pd/ZrO(2)-CeO(2) mixed oxide nanotubes with 90 mol % CeO(2) were synthesized following a very simple, high-yield procedure and their properties were characterized by synchrotron radiation X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), and scanning and high-resolution transmission electron microscopy (SEM and HRTEM). In situ XANES experiments were carried out under reducing conditions to investigate the reduction behavior of these novel nanotube materials. The Pd/CeO(2)-based nanotubes exhibited the cubic phase (Fm3m space group). The nanotube walls were composed of nanoparticles with an average crystallite size of about 7 nm, and the nanotubes exhibited a large specific surface area (85 m(2).g(-1)). SEM and HRTEM studies showed that individual nanotubes were composed of a curved sheet of these nanoparticles. Elemental analysis showed that the Ce:Zr:Pd ratios appeared to be approximately constant across space, suggesting compositional homogeneity in the samples. XANES results indicated that the extent of reduction of these materials is low and that the Ce(4+) state is in the majority over the reduced Ce(3+) state. The results suggest that Pd cations-most likely Pd(2+)-form a Pd-Ce-Zr oxide solid solution and that the Pd(2+) is stabilized against reduction in this phase. However, incorporation of the Pd (1 wt %) into the crystal lattice of the nanotubes also appeared to destabilize Ce(4+) against reduction to Ce(3+) and caused a significant increase in its reducibility.

Effect of adding CaO to ZrO(2) support on nickel catalyst activity in dry reforming of methane

Nickel catalysts with a load of 5 wt% Ni, supported on pure ZrO(2) and ZrO(2) stabilized with 4, 8 and 14 mol% CaO, were prepared by the polymerization method. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction with hydrogen (TPR-H(2)), specific surface area (BET) and impedance spectroscopy (IS) and tested in the carbon dioxide reforming of methane. The XRD patterns showed the presence of the oxide precursor (NiO) and the tetragonal phase of CaO-ZrO(2) solid solutions. According to the TPR-H(2) analysis, the reduction of various NiO species was influenced by the support composition. The electrical properties of the support have a proportional effect on the catalytic activities. Catalytic tests were done at 800 degrees C for 6 h and the composition of the gaseous products and the catalytic conversion depended on the CaO-ZrO(2) solid solution composition and its influence on supported NiO species. A direct relation was found between the variation in the electrical conductivity of the support, the nickel species supported on it and the performance in the catalytic tests. (C) 2009 Elsevier B.V. All rights reserved.

Co/Mg/Al hydrotalcite-type precursor, promoted with La and Ce, studied by XPS and applied to methane steam reforming reactions

Catalysts` precursor of Co/Mg/Al promoted with Ce and La were tested in the steam reforming of methane (SRM). The addition of promoters was made by anion-exchange. The oxides characterization was made by X-ray Photoelectron Spectroscopy (XPS) analysis that confirmed Co(2+) species in free form on surface and interacted with Mg and Al in the form of solid solution. In the SRM with high fed molar ratio of H(2)O:CH(4) = 4:1, the catalysts showed a great affinity with water and immediately deactivated by oxidation of the active sites. In the stoichiometric ratio of H(2)O:CH(4) = 2: 1 the catalysts were active and presented low carbon deposition during the time reaction tested. Also a test with low fed molar ratio H(2)O:CH(4) = 0.5:1 was carried out to evaluate the stability of the catalysts by CH(4) decomposition and all the catalysts were stable during 6 h of reaction. Promoted catalysts presented lower carbon deposition. (C) 2009 Elsevier B. V. All rights reserved.

Effect of the Y(2)O(3)-ZrO(2) support composition on nickel catalyst evaluated in dry reforming of methane

Nickel catalysts with a load of 5 wt.% Ni, supported on pure ZrO(2) and ZrO(2) stabilized with 4 mol%, 8 mol% and 12 mol% of Y(2)O(3), were prepared by the polymerization method. The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction with hydrogen (TPR-H(2)), specific surface area (BET) and electronic paramagnetic resonance (EPR) and tested as catalysts for carbon dioxide reforming of methane. The XRD patterns showed the presence of the oxide precursor (NiO) and the tetragonal phase of a Y(2)O(3)-ZrO(2) solid solution. According to the TPR-H(2) analysis, the reduction of various NiO species was influenced by the composition of the support. Catalytic tests were conducted at 800 degrees C for 6 h, and the composition of the gaseous products and the catalytic conversion rate depended on the composition of the Y(2)O(3)-ZrO(2) solid solution and its influence on the supported NiO species. A direct relation was observed between the variation in the support, the nickel species supported on it and the performance in the catalytic tests. (C) 2008 Elsevier B.V. All rights reserved.

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Solid dispersions with hydrogenated castor oil increase solubility, dissolution rate and intestinal absorption of praziquantel

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermal and electrochemical study of solid-state reaction of mercury with Pt-20% Rh alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Aspects of solid state formation and properties of Sn(0.9)Ti(0.1)O(2) system doped with CoO and Nb(2)O(5)

The effect of calcination temperature during the formation of the solid solution Sn(0.9)Ti(0.1)O(2) doped with 1.00 mol % CoO and 0.05 mol % Nb(2)O(5) is presented. The structural characteristics of this system were studied using X-ray diffraction, and the changes in phase formation were analyzed using the Rietveld method. With an increase in calcination temperature, there is increasing miscibility of Ti into the (Ti,Sn)O(2) phase and near 1000 degrees C, and the remaining TiO(2) (anatase) was transformed into the rutile phase. The sintering process, monitored using dilatometry, suggests two mass transport mechanisms, one activated close to 900 degrees C associated with the presence of TiO(2) (anatase) and the second mechanism, occurring between 1200 and 1300 degrees C, is attributed to a faster grain boundary diffusion caused by oxygen vacancies. (C) 2008 International Centre for Diffraction Data.

Structural studies on lead-cadmium fluoride solid solutions

(1-x)PbF2-(x)CdF2 solid solutions (with 0.1 less than or equal to x less than or equal to 0.5) were obtained by hyper-quenching the melt. Structural characteristics have been studied by X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS). A cubic solid solution was obtained in which the lattice parameter decreases with increasing CdF2 content. High anionic disorder was evidenced from EXAFS investigations, whereas cations remain in the FCC arrangement. Pb L-3-edge EXAFS results illustrate clearly the occurrence of CdxPb1-xF2 mixed crystals by the introduction of Cd atoms in the second Pb coordination shell. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

Solid-state reactions of mercury with pure noble metals - Part 2. Mercury-iridium system

Thermogravimetry, cyclic voltammetry and other analytical techniques were used to study the reactions of mercury with pure iridium. The results allowed to suggest when subjected to heat or anodic stripping voltammetry an electrodeposited mercury film reacts with Ir substrate and at least three mass loss steps and three peaks appear in the mercury desorption process. The first two were attributed to Hg(0) species removal like a mercury bulk and a mercury monolayer. The last can be ascribed to the mercury removal from a solid solution with iridium.

Estudo das propriedades de eletrocatalisadores de Pt-Ru nanoparticulados preparados via microemulsão para oxidação de metanol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Preparação de soluções sólidas superficiais à base de alumina como catalisadores para síntese do biodiesel via rota etílica

Pós-graduação em Química - IBILCE

Thermal study of the solid-state reactions on Pt-15%Rh/Hg system

Thermogravimetry (TG), energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface and X-ray diffraction (XRD) were used for the study of solid-state reaction on Pt-15%Rh with electrodeposited mercury. The results suggest when heated the mercury film react with the Pt-15%Rh alloy to form intermetallics having different thermal stabilities indicated by three mass loss steps. The first mass loss step occurs between room temperature and 184 degrees C only the bulk Hg is removed and PtHg4, PtHg2 and RhHg2 were characterized by XRD. The second step, between 184 and 271 degrees C, was attributed to PtHg4 decomposition with formation of PtHg2 stabilized by RhHg2. The third step, between 271 and 340 degrees C, was attributed to decomposition of a solid-solution of PtHg2/RhHg2. The fourth step, between 340 and 600 degrees C, was ascribed to: (1) a thermal decomposition of PtHg2, formed by a PtHg eutectoid reaction (similar to 340 degrees C) on the surface and (2) Hg removal from a solid solution of Pt-15%Rh(Hg). (C) 2013 Elsevier B.V. All rights reserved.

Thermal behavior of Ca2+ and Cu2+ oxalates obtained by precipitation in homogeneous solution from dimethyl oxalate hydrolysis

Mixed calcium and copper oxalates, with different proportions of Ca2+ and Cu2+ ions, were precipitated by dimethyl oxalate hydrolysis in homogeneous solution. The compounds were evaluated by means of scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetry (TG), and differential thermal analysis (DTA). The results suggested quantitative precipitation without solid solution formation. From the TG and DTA curves, it was possible to evaluate the Ca2+ ion proportion in the solid phase and to confirm the precipitation of the individual species.