Ni catalyst on mixed support of CeO2-ZrO2 and Al2O3: Effect of composition of CeO2-ZrO2 solid solution on the methane steam reforming reaction

In this study, catalysts containing 5 wt.% Ni deposited on a support composed of a CeO2-ZrO2 solid solution deposited on alumina were tested in the steam reforming of methane. The supports, with various ratios of Ce to Zr, were prepared by co-precipitation of the oxide precursors, followed by calcination in synthetic air. The catalysts were then prepared by Ni impregnation of the supports. The prepared solids were characterized by temperature-programmed reduction with H-2 (TPR-H-2), in situ X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) spectroscopy. The XRD analysis confirmed the formation of a solid solution between ZrO2 and CeO2. In the catalytic tests, it was found that catalysts with higher Ce content did not exhibit deactivation during 6 h of reaction. The catalyst with highest Ce content, Ni(0.8Ce0.2Zr)AI, provided the best result, with the highest rate of conversion of methane and the lowest carbon deposition, which may be partly due to the smaller Ni-0 crystallites in this sample and also the segregated CeO2 particles may have favored H2O adsorption which could lead to higher C gasification. (C) 2012 Elsevier B.V. All rights reserved.

Partial oxidation of methane on NiO-MgO-ZrO2 catalysts

Catalysts containing mixtures of NiO, MgO and ZrO2 were synthesized by the polymerization method. They were characterized by X-ray diffraction (XRD), physisorption of N-2 (BET), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES), and then tested in the partial oxidation of methane (POM) in the presence of air (2CH(4):1O(2)) at 750 degrees C for 6 h. Among the ternary oxides, the catalyst with 40 mol% MgO showed the highest conversion rates in the catalytic processes, but also the highest carbon deposition values (48 mmol h (1)). The greater the amount of NiO-MgO solid solution formed, the higher was the conversion rate of reactants (CH4), peaking at 40 mol% of MgO. Catalysts with lower Ni content on the surface achieved a high rate of CH4 conversion into synthesis gas (H-2 + CO). The formation of more NiO-MgO solid solution seemed to inhibit the deactivation of Ni degrees during reaction. The values of the H-2/CO product ratio were generally found to be slightly lower than stoichiometric. (C) 2012 Elsevier Ltd. All rights reserved.

Surface Segregation in Chromium-Doped Nanocrystalline Tin Dioxide Pigments

Surface properties play an important role in understanding and controlling nanocrystalline materials. The accumulation of dopants on the surface, caused by surface segregation, can therefore significantly affect nanomaterials properties at low doping levels, offering a way to intentionally control nanoparticles features. In this work, we studied the distribution of chromium ions in SnO2 nanoparticles prepared by a liquid precursor route at moderate temperatures (500 degrees C). The powders were characterized by infrared spectroscopy, X-ray diffraction, (scanning) transmission electron microscopy, Electron Energy Loss Spectroscopy, and Mossbauer spectroscopy. We showed that this synthesis method induces a limited solid solution of chromium into SnO2 and a segregation of chromium to the surface. The s-electron density and symmetry of Sn located on the surface were significantly affected by the doping, while Sn located in the bulk remained unchanged. Chromium ions located on the surface and in the bulk showed distinct oxidation states, giving rise to the intense violet color of the nanoparticles suitable for pigment application.

The T-2 phase in the Nb-Si-B system studied by ab initio calculations and synchrotron X-ray diffraction

The solid solution based on Nb5Si3 (Cr5B3 structure type, D8(l), tl32, 14/mcm, No140, a=6.5767 angstrom, c=11.8967 angstrom) in the Nb-Si-B system was studied from the structural and thermodynamic point of view both experimentally and by ab initio calculations. Rietveld refinement of powder X-ray synchrotron data allowed to determine the boron to silicon substitution mechanism and the structural parameters. Ab initio calculations of different ordered compounds and selected disordered alloys allowed to obtain in addition to the enthalpy of formation of the solution, substitution mechanism and structural parameters which are in excellent agreement with the experimental data. The stability of the phase is discussed. (C) 2012 Elsevier Inc. All rights reserved.

Effects of synthesis conditions on the nanostructre of CexZr1-xO2 mesoporous ceramics.

CexZr1-xO2 (0.5 ≤ x ≤ 0.9) were synthesized with Zr and Ce chloride precursors, using the triblock copolymer Pluronic P123 and HCl (2 mol/L). The pH adjustment was performed in two ways: synthesis A used 11.4 mL of a NH4OH solution added at once to the initial mixture, composed by metal precursors and template in HCl; synthesis B was done by dripping slowly until the change of pH value (between 3 and 6). In this work, CexZr1-xO2 samples synthesized by these two processes are compared. The effects of pH values in materials characteristics were also evaluated. These samples were analysed by X-Ray Diffraction (XRD) with Rietveld refinement, and Nitrogen Adsorption/Desorption. In both processes, the studied materials presented two crystalline phases of CexZr1-xO2 solid solution: cubic and tetragonal. The synthesis A also presented a tetragonal phase of ZrO2. The average crystallite size and the Brunauer- Emmett-Teller (BET) surface area are bigger in process A. Both processes give samples with a mesoporous structure.

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

Flow-injection spectrophotometric determination of captopril in pharmaceutical formulations using a new solid-phase reactor containing AgSCN immobilized in a polyurethane resin

A simple flow-injection analysis procedure was developed for determining captopril in pharmaceutical formulations employing a novel solid-phase reactor containing silver thiocyanate immobilized in a castor oil derivative polyurethane resin. The method was based on silver mercaptide formation between the captopril and Ag(I) in the solid-phase reactor. During such a reaction, the SCN- anion was released and reacted with Fe3+, which generated the FeSCN2+ complex that was continuously monitored at 480 nm. The analytical curve was linear in the captopril concentration range from 3.0 x 10(-4) mol L-1 to 1.1 x 10(-3) mol L-1 with a detection limit of 8.0 x 10(-5) mol L-1. Recoveries between 97.5% and 103% and a relative standard deviation of 2% for a solution containing 6.0 x 10(-4) mol L-1 captopril (n = 12) were obtained. The sample throughput was 40 h(-1) and the results obtained for captopril in pharmaceutical formulations using this procedure and those obtained using a pharmacopoeia procedure were in agreement at a 95% confidence level.

Steam reforming of ethanol for hydrogen production on Co/CeO²-ZRO² catalysts prepared by polymerization method

Catalysts containing 10%Co supported on CexZr1-xO2 (0 < x < 1) were applied to ethanol steam reforming reactions. The catalysts were characterized by Raman spectroscopy, XANES-H-2 and DRS-UV-Vis. The catalytic tests were conducted at 673, 773 and 873 K, with molar ratios of H2O:ethanol = 3:1. The ethanol conversion and H-2 selectivity were temperature dependent and the association of CeO2 with ZrO2 in the support led to show a low formation of CO, due to the higher mobility of oxygen. (C) 2012 Elsevier B.V. All rights reserved.

Influence of Modifications to the Pechini Method on the Electroactivity and Stability of Pt-RuOx/C Catalysts

Since electrode electroactivity and stability depend directly on the nature, morphology, and structure of the material, we have investigated how modifications to the Pechini method during the synthesis of Pt-RuOx/C electrocatalysts affected catalyst activity. The structure and stability of the resulting materials were investigated after their submission to a large number of potential scans and to constant potential for a prolonged time period in sulfuric acid 0.5 mol L-1 and methanol 0.1 mol L-1 solution. DMFC tests were accomplished using membrane electrode assemblies (MEAs) prepared by hot-pressing a pretreated Nafion 117 membrane together with the prepared Pt-RuOx anodes and a Pt cathode (from E-TEK), in order to compare the catalytic activity of the materials prepared by different methods. The stability studies demonstrated that the catalyst whose resin/carbon support mixture was agitated in a balls mill before undergoing heat-treatment was more stable than the other prepared catalysts. The catalysts synthesized with the single resin consisting of Pt and Ru and subjected to ultrasound before heat-treatment furnished the highest power density in the single fuel cell. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.011208jes]

CuO-CeO2 catalysts synthesized in one-step: Characterization and PROX performance

PEM fuel cells seem to be the most affordable and commercially viable hydrogen-based cells, the biggest challenge being to obtain CO-free H-2 (<100 ppm) as the fuel. In this study, the use of CuO-CeO2 catalysts in preferential oxidation of CO to obtain CO-free H-2 (PROX reaction) was investigated. Ce1-xCuxO2 catalysts, with x (mol%) = 0, 0.01, 0.03, 0.05 and 0.10, were synthesized in one-step by the polymeric precursor method, to obtain a very fine dispersion and strong metal-support interaction, to favor active copper species and a preference for the PROX reaction. The results obtained from catalyzed reactions and characterization of the catalysts by XRD, Rietveld refinement, BET surface area, UV-Vis and TPR, suggest that this one-step synthesis method gives rise to catalysts with copper species selective for the PROX reaction, which reaches a maximum rate on Ce0.97Cu0.03O2 catalyst. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Structural and reduction studies of ZrO2-CeO2:Ni for application in SOFC anodes.

Zirconia-ceria solid-solutions are extensively used as promoters for three-way catalysts, which are applied in the control of NOx, CO and hydrocarbons emission from automotive exhausts. In addition, thesematerials can be used as anodes in solid oxide fuel cells (SOFCs) operated with hydrocarbons. There areonly few works on ZrO2-CeO2 ordered mesoporous materials for catalytic applications and for anodes inSOFCs. The interest in these anodes relies on the fact that ZrO2-CeO2materials are mixed ionic/electronic conductors in reducing atmosphere and, therefore, fuel oxidation is produced on its entire surface, while it only occurs in the [anode/electrolyte/gas] interface (triple-phase boundaries) for electronic conductors. In this work, a synthesis method was developed usingZr and Ce chloride precursors, HCl aqueous solution, Pluronic P123 as the structure directing agent, NH4OH to adjust the pH (3-4) and a Teflon autoclave to perform hydrothermal treatment (80ºC/48 hours). The samples were dried and calcined, until 540ºC in N2and 4 hours in air. The X-ray diffraction data showed that powders with higher CeO2 content are formed by a larger fraction of the cubic CeO2 phase, while for a lower CeO2content the major crystalline structure is the tetragonal ZrO2 phase. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)×6H2O. The resulting powder was calcinated in air until 350ºC for 2 hours. Temperature-programmed reduction (TPR) data were collected in order to evaluate the reduction profiles of ZrO2-x%CeO2:Ni samples in H2/Ar atmosphere. Results showed lower reduction temperatures for all ceria content in samples comparing to a NiO standard.

Influence of the network modifier on the characteristics of MSnO3 (M=Sr and Ca) thin films synthesized by chemical solution deposition

CaSnO3 and SrSnO3 alkaline earth stannate thin films were prepared by chemical solution deposition using the polymeric precursor method on various single crystal substrates (R- and C-sapphire and 100-SrTiO3) at different temperatures. The films were characterized by X-ray diffraction (θ-2θ, ω- and φ-scans), field emission scanning electron microscopy, atomic force microscopy, micro-Raman spectroscopy and photoluminescence. Epitaxial SrSnO3 and CaSnO3 thin films were obtained on SrTiO3 with a high crystalline quality. The long-range symmetry promoted a short-range disorder which led to photoluminescence in the epitaxial films. In contrast, the films deposited on sapphire exhibited a random polycrystalline growth with no meaningful emission regardless of the substrate orientation. The network modifier (Ca or Sr) and the substrate (sapphire or SrTiO3) influenced the crystallization process and/or the microstructure. Higher is the tilts of the SnO6 octahedra, as in CaSnO3, higher is the crystallization temperature, which changed also the nucleation/grain growth process.