Insight into Copper-Based Catalysts: Microwave-Assisted Morphosynthesis, In Situ Reduction Studies, and Dehydrogenation of Ethanol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

AC impedance study of Ni, Fe, Cu, Mn doped ceria stabilized zirconia ceramics

Doped zirconia has been used in electronic applications in the cubic crystalline phase. Ceria-stabilized tetragonal zirconia presents high toughness and can also be applied as solid electrolytes. The tetragonal phase of zirconia can be stabilized at room temperature with ceria in a broad range of composition. However, CeO2-ZrO2 has low sinterability. so it is important to investigate the effect of sintering dopants. In this study the effect of iron, copper. manganese and nickel was investigated. The dopants such as iron and copper lowered the sintering temperature from 1600 degreesC down to 1450 degreesC, with a percentage of tetragonal phase retained at room temperature higher than 98% and also with an increase of the electrical conductivity. The electrical conductivity was measured using impedance spectroscopy. The grain boundary contribution was determined and the activation energy associated with the ionic conduction was 1.04 eV. The dopants can also promote a grain boundary cleanliness verified by blocking effect measurement. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

OXIDES AS HETEROGENEOUS PROMOTERS FOR LIQUID-PHASE HYDROCARBONYLATION REACTIONS WITH IODOCARBONYLRUTHENIUM CATALYSTS

Basic or acid oxides, used as heterogeneous promoters of carbonylruthenium catalysts in liquid-phase hydrocarbonylation reactions on oxygenated substrates, strongly affect the activity and selectivity of the catalytic system. Concurrent or successive reactions of simple carbonylation, homologation, hydrogenation to hydrocarbons, and etherification take place to varying extents. Carbonylation and etherification are favored by acid oxides and homologation and hydrogenation by basic oxides. This behavior is related to the formation and stabilization by the oxides of H+ and H- hydridocarbonylruthenium catalytic species, whose relative concentrations in solution depend on the nature of the oxide. Heterogeneous oxides are easily separated and recycled from the reaction mixture. Their use simplifies the catalytic system and allows one to direct the catalytic process toward the target product.

Preparation and characterization of spherical silica-porphyrin catalysts obtained by the sol-gel methodology

This work describes the synthesis of a first-generation iron porphyrin catalyst entrapped in a silica matrix by the sol-gel route, leading to spherical particles. The catalyst was synthesized by the method of Stober, through hydrolysis and condensation of the alkoxysilane TEOS in a mixture of alcohol, water and ammonia, in the presence of the iron porphyrin Fe(TPP)Cl. The relation between particle morphology and catalytic activity of the different Fe(TPP)-SiO2, obtained using different H2O/silane molar ratios and ammonia concentrations in the xerogel syntheses, was studied.The obtained catalysts were characterized by UV-vis spectroscopy, NMR Si-29. thermogravimetric analysis and transmission electron microscopy. Their ability to catalyze (Z)-cyclooctene epoxidation and cyclohexane oxidation was tested using iodosylbenzene as oxygen donor; the oxidation products were analyzed by gas chromatography and the catalysts obtained in a form of particles spherical and monodispersed showed to be a promising catalytic system for selective oxidation. (c) 2005 Elsevier B.V. All rights reserved.

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (> 50 wt.%). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications.

Effect of ceria content on the sintering of ZrO2 based ceramics synthesized from a polymeric precursor

Zirconia-ceria powders with ceria concentration varying from 0 to 12 mol% were synthesized using a polymeric precursor route based on the Pechini process. Powder characteristics were evaluated with regard to the crystallite size, BET surface area, phase distribution, nitrogen adsorption/desorption behavior, and agglomeration state. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. It was demonstrated that the synthesis method is effective to prepare nanosized powders of tetragonal zirconia single-phase. Sinterability mainly depended on the agglomeration state of powders and the monoclinic phase content, fully tetragonal zirconia ceramic, with grain size of 2.4 mu m, was obtained after addition of at least 9 mol% ceria and sintering at 1500 degrees C for 4 h. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

Electrical measurements in doped zirconia-ceria ceramics

Zirconia-ceria powders with 12 mol % of CeO2 doped with 0.3 mol% of iron, copper, manganese and nickel oxides were synthesized by the conventional mixed oxide method. These systems were investigated with regard to the sinterability and electrical properties. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. Small amount of dopant such as iron reduces sintering temperature by over 150degreesC and more than 98% of tetragonal phase was retained at room temperature in samples sintered at 1450degreesC against 1600degreesC to stabilize the tetragonal phase on pure ZrO2-CeO2 system. The electrical conductivity was measured using impedance spectroscopy and the results were reported. The activation energy values calculated from the Arrhenius's plots in the temperature range of 350-700degreesC for intragrain conductivities are 1.04 eV.

Effect of substitution of [Pd(PPh3)(4)] by related compounds as catalysts in reactions of organic syntheses

The effect of substitution of [Pd(PPh3)(4)], which is unstable in air, by complexes of the type [MCl2L2] (M = Pd, Pt; L = AsPh3, SbPh3), [PdL4](L = PPh3, AsPh3, SbPh3) and [NiX2(PPh3)(2)] on the syntheses of thioethers, acetylenes and ketones is described.

Densification and electrical conductivity of fast fired manganese-doped ceria ceramics

Reactive pure and manganese-doped (5% and 10 at.%) ceria nanosized powders were prepared by the polymeric precursor technique. Physical properties of powder materials were studied by X-ray diffraction, nitrogen adsorption, and diffuse reflectance infrared Fourier transform spectroscopy. Characterization of powder compacts after fast firing at 1200 degrees C for 5 min was carried out by scanning electron microscopy and impedance spectroscopy measurements. The bulk apparent density of sintered pellets was determined for pellets of different compositions sintered at 1200 degrees C. A gradual decrease of the particle size occurs with increasing doping content. Relatively high values of apparent density were obtained after fast firing doped specimens at 1200 degrees C. DRIFT spectra evidence that a fraction of Mn ions was segregated onto particles surface. The electrical resistivity of sintered pellets reveals different mechanisms of conduction depending on the Mn content. (C) 2005 Elsevier B.V All rights reserved.

Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

The reaction of TlTp' (Tp' = HB(3-mesitylpyrazolyl)(3)(-) (Tp(Ms)), HB(3-mesitylpyrazolyl)(2)(5-mesitylpyrazolyl)(-) (Tp(Ms)*)) with NiCl(2).6H(2)O affords Tp(Ms)NiCl (1) and Tp(Ms)*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{Tp(Ms)**}NiCl](2) (3) (Tp(Ms)** = HB(5-mesitylpyrazolyl)(2)(3-mesitylpyrazolyl)(-)) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2-43.1) x 10(3) h(-1). Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.

Niobium to alcohol mol ratio control of the concurring esterification and etherification reactions promoted by NbCl5 and Al2O3 catalysts under microwave irradiation

Alcohols and acids can be switched to produce ethers or esters by varying the alcohol to catalyst mol ratio, in a new etherification and esterification method using NbCl5/Al2O3 catalyst under "solvent free" conditions and promoted by MW (microwave) irradiation. A "two sites" mechanism for the reaction is proposed, in an attempt to clarify the tendency of the catalyst to be dependent on the alcohol alone during the esterification process. (c) 2008 Elsevier B.V. All rights reserved.

Preparation and characterization of ceria nanospheres by microwave-hydrothermal method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Improved activity and stability of Ce-promoted Ni/γ-A1 2O3 catalysts for carbon dioxide reforming of methane

The CO2 reforming of CH4 was carried out over Ni catalysts supported on γ-Al2O3 and CeO 2-promoted γ-Al2O3. The catalysts were characterized by means of surface area measurements, TPR, CO2 and H2 chemisorption, XRD, SEM, and TEM. The CeO2 addition promoted an increase of catalytic activity and stability. The improvement in the resistance to carbon deposition is attributed to the highest CO2 adsorption presented by the CeO2 addition. The catalytic behavior presented by the samples, with a different CH4/CO2 ratio used, points to the CH4 decomposition reaction as the main source of carbon deposition.

Functional nanostructured catalysts based on the niobates to the dry methane reforming and ethylene homologation reactions

Catalytic activity and selectivity of niobate-based nanostructured materials were investigated. Dry methane reforming (DMR) and ethylene homologation reaction (EHR) were selected as test reactions. KSr 2Nb5O15, Sr2NaNb5O 15 and NaSr2(NiNb4)O15 δ niobate powders were prepared by the high energy ball milling method and calcined in a reductor atmosphere. N2 adsorption isotherms, X-ray diffraction and infrared spectroscopy characterization was performed. Hydrogen pretreated niobates showed from low to moderate catalytic initial activity in DMR's test, nevertheless the materials were deactivated rapidly and the kinetic parameters associated to deactivation were estimated. Otherwise, non-treated catalysts showed a high initial activity in EHR's test and KSr2Nb 5O15 catalyst requires 24 h to the total deactivation with a high selectivity to form propylene. A reaction mechanism to the propylene formation is discussed. © 2012 Elsevier Ltd. All rights reserved.