Determinação de diagramas de bandas de energia e da borda de absorção em SnO2, depositado via sol-gel, sobre quartzo

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

Sol-gel synthesis of titania-alumina catalyst supports

Titanium oxide is a good candidate as new support for hydrotreating (HDT) catalysts, but has the inconvenience of presenting small surface area and poor thermal stability. To overcome these handicaps TiO2-Al2O3 mixed oxides were proposed as catalyst support. Here, the 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, chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal complexing ratios [acac]/[Ti] and of sol aging temperature on the structural features of nanometric particles was analyzed by quasi-elastic light scattering (QELS) and N-2 adsorption isotherm measurements. These characterizations have shown that the addition of acac and the increase of aging temperature favor the full dispersion of primary nanoparticles in mother acid solution. The dried powder presents a monomodal distribution of slit-shaped micropores, formed by irregular packing of platelet primary particles, surface area superior to 200 m(2) g(-1) and mean pore size of about 1 nm. These characteristics of porous texture are preserved after firing at 673 K. The diffraction patterns of sample fired above 973 K show only the presence of anatase crystalline phase. The crystalline structure of the support remained unaltered after molybdenum adsorption, but the surface area and the micropore volume were drastically reduced. (C) 2002 Published by Elsevier B.V. B.V.

Nanocrystalline anatase thin films prepared from redispersible sol-gel powders

Transparent thin films of nanocrystalline anatase were obtained by dip-coating process using an ethanolic suspension of redispersed nanoparticles. This suspension was prepared by sol-gel route and their redispersability achieved by surface grafting of para-toluene-sulfonic acid and acetylacetone. The effects of the acetylacetone content on the powder redispersibility and on the structural evolution of films were determined by small angle X-ray scattering, X-ray reflectometry and X-ray diffraction for different firing temperatures. The results demonstrated that the porous structure of the studied films consist of agglomerates of primary particles with two levels of porosity. The control of the amount of capping ligand allows for a fine-tuning of the average pore size of the dried films. Upon increasing the firing temperature up to 500 degrees C, progressive increase in apparent density, average pore size of films and average crystallite size of powders were observed. (c) 2005 Elsevier Ltd. All rights reserved.

Photoelectrochemical properties of sol-gel Nb2O5 films

Structural, optical, electro and photoelectrochemical properties of amorphous and crystalline sol-gel Nb2O5 coatings have been determined. The coatings are n-type semiconductor with indirect allowed transition and present an overall low quantum efficiency (phi < 4%) for UV light to electric conversion. The photoconducting behavior of the coatings is discussed within the framework of the Gartner and Sodergren models. Improvement can be foreseen if Nb2O5 coatings can be made of 10-20 nm size nanoparticles.

Effect of aging on the stability of ceramic foams prepared by thermostimulated sol-gel process

This work presents a new route of preparation of zirconium ceramic foams based on the thermostimulated sol-gel process. This method produces gelled bodies with up to 90% of porosity in the wet gel and can be used to make complex-shaped components. Unfortunately, the shrinkage during the drying step allows to a catastrophic reduction (50%) of the foam porosity. To improve the foam stability we carried out a systematic study of the effect of gel foam aging on the drying process. Samples were aged in closed vessel at 25 C during different time period (from 6 to 240 h). The shrinkage and the mass loss during drying at 50 C were measured in situ, using a non-contact technique performed with a special apparatus. The results show that the total linear shrinkage decreases from 46% to 8% as the aging period increase from 6 to 240 h. This behavior is followed by a small change of total mass loss, from 42 to 54%. It indicates that by aging the structural stiffness of the foams increases due to secondary condensation reactions. Thus, by controlling the aging period, the porosity can be increased from 67 to 75% and the average size of mesopores of dried foams can be screened from 0.3 to 0.9 mum. Finally, these results demonstrate that the thermostimulated sol-gel transition provides a potential route to ceramic foams manufacture.

Formation of zirconia foams using the thermostimulated sol-gel transition

In this paper we describe the production of zirconia-based foams by a novel thermostimulated sol-gel route, that employs the foaming of colloidal suspensions prior to the sol-gel transition promoted by small increase of temperature (congruent to3 degreesC). This method produces gelled bodies having porosity >70% in the wet stage, and can be used to produce complex-shaped components. The effect of a foaming agent (Freon11 or CCl3F) and surfactant content on the formation and stability of the foams was analyzed. The rheologic measurements demonstrate that by increasing the surfactant concentration, the gelation time decreases increasing foam stability. As the surfactant concentration and quantity of foaming agent increase, the density decreases and the porosity increases. Hg porosimetry results show that the dry foam presents a bimodal pore size distribution. The family of sub-micrometer pores was attributed to the formation of a microemulsion between Freon11 and water. Scanning electron microscopy analysis shows that the foam structure consists of a three-dimensional network of spherical pores, which may be open and interconnected or closed, at larger or smaller porosities, respectively. Finally these results show that the thermostimulated sol-gel transition provides a potential route for ceramic foam manufacture. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Ultraviolet excitation of photoconductivity in thin films of sol-gel SnO2

Tin dioxide (SnO2) thin film photoconductivity spectra were measured for a large temperature range using a deuterium source, the intensity of photocurrent spectra in the range 200-400 nm is temperature dependent, and the photocurrent increases in the ultraviolet even for illumination with photon energies much higher than the bandgap transition. This behavior is related to recombination of photogenerated electron-hole pairs with oxygen adsorbed at grain boundaries, which is consistent with nanoscopic crystallite size of sol-gel deposited films. (c) 2005 Elsevier Ltd. All rights reserved.

O processo sol-gel: uma visão físico-química

The aim of this work was to revise the main concepts involved in the physical-chemistry of the sol-gel process. First, the preparation and its influence on the gel's structure are focalized; the sol-gel transition is revised under the thermodynamics of crytical phenomena point of view and by considering the kinetic models of aggregation. Second, the experimental methods usually used to characterize the sol-gel transition are discussed.

Characterization of the porosity developed in a new titania-alumina catalyst support prepared by the sol gel route

Titanium oxide (TiO2) is a good candidate for support of hydrotreating catalysts but has the disadvantage of presenting a low surface area and a poor thermal stability when compared with Al2O3. A mixed TiO2-Al2O3 support was proposed as an alternative that is expected to be free from these drawbacks. The variation during firing of the nanoporous texture of supports composed of TiO2-Al2O3, TiO2 and Al2O3 was studied by small angle X-ray scattering (SAXS). The supports were prepared by the sol-gel route using Ti and Al isopropoxides. We have particularly analyzed the effects of acid and basic hydrolysis on the nanostructural features of catalyst supports fired at different temperatures. The nanopore radius distribution functions were determined from SAXS results assuming a simple model of spherical nanopores embedded in a homogeneous solid matrix. The modal pore radius in both pure TiO2 and pure Al2O3 supports grows from 1.3 to 2.2 nm as the firing temperature increases from 673 to 973 K. on the other hand, the modal pore radius in the mixed TiO2-Al2O3 support remains below 1.2 nm over the same range of firing temperatures. These results demonstrate the good thermal stability of the nanoporous texture of mixed TiO2-Al2O3 supports.

Study of structural surface modified tin oxide membrane prepared by sol-gel route sintered at 400 degrees C

This work describes the chemical modification by Tiron(R) molecules of the surface of SnO2 nanoparticles used to prepare nanoporous membranes. Samples prepared with Tiron(R) content between 1 and 20 wt% and fired at 400 C were characterised by X-Ray Powder Diffraction (XRPD), Extended X-ray Absorption Fine Structure (EXAFS), N-2 adsorption isotherms analysis and permeation experiments. XRPD and EXAFS results show a continuous reduction of crystallite size by increasing the Tiron(R) contents until 7.5 wt%. The control exercised by Tiron(R) modifying agent in crystallite growth allows the fine tuning of the average pore size that can be screened from 0.4 to 4 nm as the amount of grafted molecules decreases from 10 to 0 wt%. In consequence, the membrane cut-off can be screened from 1500 to 3500 g.mol(-1).

Functionalized silica synthesized by sol-gel process

This work considers some aspects of the chemistry involved in the preparation and description of silicon oxide functionalized by sol-gel process. In this work we studied the synthesis and measured the properties of silicon oxide functionalized with 3-chloropropyl, through a sol-gel process. Thermogravimetic analysis, infrared spectra, and elemental analyses were measured. The samples were prepared in the following proportions of tetraethylorthosilicate (TEOS): 3-chloropropyl trimethoxisilane molar ratio: 1:0, 1:1, 2:1, 3:1 and 4:1. The thermogravimetric data for the resulting materials established the 'minimum formulae' 2:0, 3:1, 4.1, 7:1 and 11:1, respectively. As expected, the relative amount of water is inversely proportional to the presence of propyl groups. Infrared data show Si-C and -CH2-vibration modes at 1250 to 1280 and 2920 to 2940 cm(-1), respectively. Thermogravimetric data and infrared spectra showed that inorganic polymers contained organic polymers. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Small angle X-ray scattering study of surface modified tin oxide nanoparticles prepared by sol-gel route

The surface properties of SnO2 nanoparticles were modified by grafting ionic (Tiron (R). (OH)(2)C6H2(SO3Na)(2)(H2O)-H-.) or non-ionic (Catechol (R). C6H4-1,2-(OH)(2)) capping Molecules during aqueous sol-gel processing to improve the redispersibility of powdered xerogel. The effect of the amount of grafted organic molecules on the redispersibility of powders in aqueous solution at several basic pH values was Studied. The nanostructural features of the colloidal suspensions were analyzed by small angle X-ray scattering (SAXS) measurements. Irrespective of the nature and amount of grafted molecules, complete redispersion was obtained in aqueous solution at pH = 13. The redispersion at pH = 11 results in a mixture of dispersed primary particles and aggregates. The proportion of well dispersed nanoparticles and aggregates (and their average size) can be tuned by the quantity of grafted ionic molecules.

Microwave synthesis of YAG : Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl3, YCl3 and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800 C during I h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 C. For the samples pretreated at 800 degrees C, the YAG phase appears in 30s. The excitation spectra present a maximum of 394 nm corresponding to the L-5(6) level and emission spectra of Eu III ion present bands characteristic transitions arising from the D-5(0) -> F-7(J) (J= 1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole D-5(0) -> F-7(1) transition presents more intensity than the electric dipole D-5(0) -> F-7(2) transition. This methodology showed efficiency in obtaining YAG phase. (c) 2006 Elsevier B.V. All rights reserved.

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.

X-ray reflectivity of zirconia based sol-gel coatings on borosilicate glasses

In this work the technique of X-ray reflectometry was applied to study zirconiumsulfate films deposited by sol-gel dip-coating process on a borosilicate glass surface. The influence of withdrawal speed and temperature of thermal treatment on the film structure are analyzed. The thermal evolution of the density and thickness of the film was compared with these properties measured for a monolithic xerogel by helium picnometry and thermomechanical analysis. The fitting of experimental curves by classical reflectivity model showed the presence of an additional layer at the top surface of the coating. Layer thickness increases with increase of withdrawal speed in agreement with the Landau-Levich model. The apparent and real densities are similar for coatings fired below 400 degrees C, which shows that the films are free of pores. The shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface. (C) 1999 Elsevier B.V. B.V. All rights reserved.