Improvement of the Mo/TiO2-Al2O3 catalyst by the control of the sol-gel synthesis

Traditional hydrotreating catalysts are constituted by molybdenum deposited on Al2O3 promoted by nickel and phosphorous. Several studies have shown that TiO2-Al2O3 mixed oxides are excellent supports for the active phases. Results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, the titanium one chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal molar ratio [Ti]/[Ti+Al] on the microstructural features of nanometric particles was analyzed by X-Ray Diffraction, N-2 Adsorption Isotherms and Transmission Electron Microscopy. The catalytic activity of Mo impregnated supports was evaluated using the thiophene hydrodesulfurization at different temperatures and atmospheric pressure. The pores size distribution curve moves from the micropores to the mesopores by increasing the Ti contents, allowing the fine tuning of average size from 2.5 to 6 nm. Maximal (367 m(2).g(-1)) and minimal (127 m(2).g(-1)) surface area were found for support containing [Ti]/[Ti+Al] ratio equal to 0.1 and 1, respectively. The good mesopore texture of alumina-titania support with [Ti]/[Ti+Al] molar ratio between 0.3 and 0.5 was found particularly valuable for the preparation of well dispersed MoS2 active phase, leading to HDS catalyst with somewhat higher activity than that prepared using a commercial alumina support.

pH at the micellar interface: Synthesis of pH probes derived from salicylic acid, acid-base dissociation in sodium dodecyl sulfate micelles, and Poisson-Boltzmann simulation

The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of' the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl Sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate- 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate-, 2-hydroxy-5-(2-diniethylhexadecylammoniumundecanoyl)betizoate; 2-hydroxy-5-acetylbenzoic acids and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pKap. The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of' the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pKap's of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis. (c) 2005 Elsevier B.V. All rights reserved.

Dielectric properties of Na1-xLixNbO3 ceramics from powders obtained by chemical synthesis

Ultra-fine powders of Na1-xLixNbO3 (x=0; 0.06; 0.09; 0.12) were synthesized by the Polymeric Precursors Method. Such powders had their orthorhombic structures determined by X-ray diffraction and their surface area determined by BET isotherms (less than 10 m(2) g(-1)). Densification was followed by dilatometric study. The powders, calcined at 700 degrees C for 5 h, were sintered at 1290 degrees C during 2 h under ambient atmosphere with no application of extra pressure. The samples with relative densities higher than 95% were analyzed by impedance spectroscopy at room temperature, under a signal amplitude of 1 V-rms. Dielectric constants of about 180 and dielectric loss factor of about 0.03 were measured showing small dependence with frequency. The electrical properties were similar to those obtained for samples sintered by hot pressing. (C) 1999 Elsevier B.V. Limited and Techna S.r.l. All rights reserved.

Synthesis by the polymeric precursor method and characterization of undoped and Sn, Cr and V-doped ZrTiO4

In this work, zirconium titanate doped with 0. 1, 0.2, and 0.4 mole% of tin, chromium and vanadium was synthesized by the polymeric precursors method and characterized by thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen adsorption and scanning electronic microscopy (SEM). The powder presented two mass losses attributed to the exit of water and to the pyrolysis of the organic material. The surface area reduction observed from 500 degrees C indicates the beginning of the sintering process. All the dopants led to changes in the lattice parameters and to the decrease of both crystallite size and particle size. (c) 2005 Elsevier B.V. All rights reserved.

Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

Mechanochemical synthesis of PZT powders

PZT ceramic powders were successfully prepared from the mixture of PbO, ZrO2 and TiO2 by mechanochemical synthesis in a planetary ball mill, under different milling conditions. Phase evolution during synthesis was monitored by X-ray diffraction analysis. Intensive milling resulted in formation of the nanocrystalline, perovskite PZT powders after 1 h of milling. This is a significant improvement in comparison to milling conditions reported by other authors. Depending on milling parameters the presence of some other phases, such as unreacted ZrO2, was also detected in some samples. The changes in powder size and morphology due to intensive milling, were determined by SEM and TEM, while BET analysis was used to determine specific surface area of the powders. Conclusions about processes taking place during mechanochemical synthesis of PZT powders were made based on the results of characterization. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Microwave synthesis of calcium bismuth niobate thin films obtained by the polymeric precursor method

The crystal structure, surface morphology and electrical properties of layered perovskite calcium bismuth niobate thin films (CaBi2Nb2O9-CBN) deposited on platinum coated silicon substrates by the polymeric precursor method have been investigated. The films were crystallized in a domestic microwave and in a conventional furnace. X-ray diffraction and atomic force microscopy analysis confirms that the crystallinity and morphology of the films are affected by the different annealing routes. Ferroelectric properties of the films were determined with remanent polarization P-r and a drive voltage V-c of 4.2 mu C/cm(2) and 1.7 V for the film annealed in the conventional furnace and 1.0 mu C/cm(2) and 4.0 V for the film annealed in microwave furnace, respectively. A slight decay after 10(8) polarization cycles was observed for the films annealed in the microwave furnace indicating a reduction of the domain wall mobility after interaction of the microwave energy with the bottom electrode. (C) 2006 Elsevier Ltd. All rights reserved.

Synthesis, characterization and electropolymerization of a new polypyrrole iron(II) Schiff-base complex

This work presents the synthesis of the complex [Fe(L)(2)](PF6)(2) (.) H2O (L = 2,6-bis[1-(3-pyrrol-1-yl-propylimino)ethyl]pyridine (Fig. 1) and its characterization through elemental and thermal analysis, X-ray diffraction and UV-Vis, IR and H-1 NMR spectra. The use of this compound in the preparation of modified electrodes is also described. The best electrochemical parameters to achieve optimum film formation have been established and the effects of both the upper-limit of the applied scanning potential (E-aul) and the number of scans on the efficiency of film formation have been investigated. Film surface morphology has been characterized by atomic force microscopy. (C) 2004 Elsevier Ltd. All rights reserved.

Low temperature synthesis and electrical properties of PbTiO3 thin films prepared by the polymeric precursor method

Ferroelectric PbTiO3 thin films were successfully prepared on a Pt(111)Ti/SiO2/Si(100) substrate for the first time by spin coating, using the polymeric precursor method. X-ray diffraction patterns of the films indicate that they are polycrystalline in nature. This method allows low temperature (500 degrees C) synthesis and high electrical properties. The multilayer PbTiO3 thin films were granular in structure with a grain size of approximately 110-120 nm. A 380-nm-thick film was obtained by carrying out four cycles of the spin-coating/heating process. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness (=3.4 nm). At room temperature and at a frequency of 100 kHz, the dielectric constant and the dissipation factor were, respectively, 570 and 0.016. The C-V characteristics of perovskite thin film prepared at low temperature show normal ferrolectric behavior. The remanent polarization and coercive field for the films deposited were 13.62 mu C/cm(2) and 121.43 kV/cm, respectively. The high electrical property values are attributed to the excellent microstrutural quality and chemical homogeneity of thin films obtained by the polymeric precursor method. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Synthesis of nanocrystalline tetragonal zirconia by a polymeric organometallic method

A polymeric precursor method based on the Pechini process was successfully used to synthesize zirconia-12 mol% ceria ceramic powders, the influence of the main process variables (citric acid-ethylene glycol ratio, citric acid-total oxides ratio and calcination temperature) on phase formation and powder morphology (surface area and crystallite size) were investigated. The thermal decomposition behavior of the precursor is presented. X-ray diffraction (XRD) patterns of powders revealed a crystalline tetragonal zirconia single-phase, with crystallite diameter ranging from 6 to 15 nm. The BET surface areas were relatively high, reaching 95 m(2) g(-1) Nitrogen adsorption/desorption on the powders suggested that nonaggregated powders could be attained, depending on the synthesis conditions. Copyright (C) 1999 John Wiley & Sons, Ltd.

Low-temperature synthesis of single-phase Co7Sb2O12

Polycrystalline Co7Sb2O12 compounds have been synthesized by a chemical route, which is based on a modified polymeric precursor method. In order to study the physical properties of the samples, X-ray diffraction (XRD), thermal analyses (TG and DSC), infrared spectroscopy (IR), specific surface area (BET), and magnetization measurements were performed on these materials. Characterization through XRD revealed that the samples are single-phase after a heat-treatment at 1100degreesC for 2h, while the X-ray patterns of the samples heat-treated at lower temperatures revealed the presence of additional Bragg reflections belonging to the Co6Sb2O6 phase. These data were analyzed by means of Rietveld refinement and further analyze showed that Co7Sb2O12 displays an inverse spinel crystalline structure. In this structure, the Co2+ ions occupy the eight tetrahedral positions, and the sixteen octahedral positions are randomly occupied by the Sb5+ and Co2+ ions. IR studies disclosed two strong absorption bands, v(1) and v(2), in the expected spectral range for a spinel-type binary oxide with space group Fd3m. Exploratory studies concerning the magnetic properties indicated that this sample presents a spin-glass transition at T-f similar to 64 K. (C) 2004 Elsevier B.V. All rights reserved.

Preparation and characterization of nanosized SrBi2Nb2O9 powder by the combustion synthesis

This work presents the preparation of SrBi2Nb2O9 (SBN) directly by the combustion synthesis. Strontium nitrate, niobium ammonium oxalate (NH4H2[NbO-(C2O4)(3)].3H(2)O) and bismuth oxide were used as oxidant reactants and urea as fuel. The influence of the fuel was evaluated by the addition of different fuel amounts (50%, 100%, 200% and 300%), 100% being the stoichiometric proportion. The XRD patterns showed that the SBN perovskite crystallized as the majority phase. The as-synthesized stoichiometric powder presented a specific surface area of around 13 m(2)/g and a mean grain size of around 16 nm. Dilatometric measurements showed that the maximum sintering rate occurs at 1275degreesC. The determination of the ferroparaelectric transition showed a Curie temperature (T-c) of 429degreesC. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis

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

Synthesis, ferroelectric and optical properties of (Pb,Ca)TiO3 thin films by soft solution processing

Calcium modified lead titanate sol was synthesized using a soft solution processing, the so-called polymeric precursor method. In soft chemistry method, soluble precursors such as lead acetate trihydrate, calcium carbonate and titanium isopropoxide, as starting materials, were mixed in aqueous solution. Pb0.7Ca0.3TiO3 thin films were deposited on platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure, dielectric and optical properties of the thin films were investigated. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 299 and 0.065, respectively, for a thin film with 230 nm thickness annealed at 600degreesC for 2 h. The remanent polarization (2P(r)) and coercive field (E-c) were 32 muC/cm(2) and 100 kV/cm, respectively. Transmission spectra were recorded and from them, refractive index, extinction coefficient, and band gap energy were calculated. Thin films exhibited good optical transmissivity, and had optical direct transitions. The present study confirms the validity of the DiDomenico model for the interband transition, with a single electronic oscillator at 6.858 eV. The optical dispersion behavior of PCT thin film was found to fit well the Sellmeir dispersion equation. The band gap energy of the thin film, annealed at 600degreesC, was 3.56 eV. The results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of PCT thin films.