Morphology and topography analysis of mesoporous titania templated by micrometric latex sphere arrays

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

Hexagonal mesoporous silica modified with 2-mercaptothiazoline for removing mercury from water solution

A method for the attachment of 2-mercaptothiazoline (MTZ) to modified silica gel has been developed. In the first step, a new silylant agent was synthesized, named SiMTZ, by the reaction between MTZ molecule and chloropropyltrimethoxysilane (SiCl). SiMTZ and tetraethylortosilicate were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified ordered hexagonal mesoporous silica named HMTZ. The modified material contained 0.89 +/- 0.03 mmol of 2-mercaptothiazoline per gram of silica. FT-IR, FT-Raman, Si-29- and C-13-NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. HMTZ material has been used for divalent mercury adsorption from aqueous solution at 298 I K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles of mercury adsorbed gave 2.34 +/- 0.09 mmol/g of material. The same interaction was followed by calorimetric titration on an isoperibol calorimeter. The HMTZ presented a high capacity for the removal of the contaminant mercury from water. The Delta H and Delta G values for the interaction were determined to be -56.34 +/- 1.07 and -2.14 +/- 0.11 kJ mol(-1). This interaction process was accompanied by a decrease of entropy value (- 182 J mol(-1) K-1). Thus, the interaction between mercury and HMTZ resulted in a spontaneous thermodynamic system with a high favorable exothermic enthalpic effect. (c) 2007 Elsevier B.V. All rights reserved.

Electrochemical study of o-toluidine blue impregnated in mesoporous silica channels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Rhodamine 6G encapsuled mesoporous silica channels

We report the effect of solvent on the rhodamine 6G encapsuled into channels of mesoporous silica, synthesized by two-step process that gives intermediary stable hybrid micelles. Mesoporous materials have been obtained by the method that involves surfactant micelles (mainly cationic) and inorganic precursor of the structure to be obtained. MSU-X type mesoporous silica has been synthesized with polyethylene oxide surfactant as the directing-structure agent and tetraethyl orthosilicate Si(OEt)(4) as the silica source. The influence of the solvent on the encapsulation of rhodamine dye was systematically explored, specially its influence on the luminescence properties. Rhodamine 6G encapsuled into mesoporous silica channel was characterized by UV-Vis and luminescence spectroscopies, scanning electron microscopy, small angle x ray scattering and N(2) sorption-desorption. The pore size and the solvent effects into luminescence dye encapsuled into mesoporous silica channels are observed in the visible absorption and emission spectra of rhodamine 6G. The intense photo luminescence band of rhodamine 6G dye is in 500 to 600 nm region. The observed shift of the absorption and emission bands can be assigned to the effect of the solvents dielectric constant and pore size of mesoporous silica.

Characterization of silica-carbon mesoporous matrix with embedded nickel nanoparticles synthesized by the polymeric precursor method

Nickel nanoparticles into silica-carbon matrix composites were prepared by using the polymeric precursor method. The effects of the polyester type and the time of pyrolysis on the mesoporosity and nickel particle dispersion into non-aqueous amorphous silica-carbon matrix were investigated by thermogravimetric analysis, adsorption/desorption isotherms and TEM. A well-dispersed metallic phase could be only obtained by using ethylene glycol. Weightier polyesters affected the pyrolysis process due to a combination of more amounts of carbonaceous residues and delaying of pyrolysis process. The post-pyrolyzed composites were successfully cleaned at 200 degrees C for I h in oxygen atmosphere leading to an increase in the surface area and without the occurrence of carbon combustion or nickel nanoparticles oxidation. The matrix composites presented predominantly mesoporous with pore size well defined in 38 angstrom, mainly when tetraethylene glycol was used as polymerizing agent. (C) 2007 Elsevier B.V. All rights reserved.

Production of biodiesel by esterification of palmitic acid over mesoporous aluminosilicate Al-MCM-41

Biodiesel has been obtained by esterification of palmitic acid with methanol, ethanol and isopropanol in the presence of Al-MCM-41 mesoporous molecular sieves with Si/Al ratios of 8.16 and 32. The catalytic acids were synthesized at room temperature and characterized by atomic absorption spectrometry (AAS), thermal analysis (TG/DTA), X-ray diffraction (XRD), nitrogen absorption (BET/BJH), infrared spectroscopy (IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The reaction was carried out at 130 degrees C whilst stirring at 500 rpm, with an alcohol/acid molar ratio of 60 and 0.6 wt% catalyst for 2 h. The alcohol reactivity follows the order methanol > ethanol > isopropanol. The catalyst Al-MCM-41 with ratio Si/Al = 8 produced the largest conversion values for the alcohols studied. The data followed a rather satisfactory approximation to first-order kinetics. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis and characterization of mesoporous TiO2 nanostructured films prepared by a modified sol-gel method for application in dye solar cells

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.

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.

Titania-based organic-inorganic hybrid planar waveguides

Eu3+ -doped titania-silica planar waveguides were prepared from tetraethylorthotitanate (TEOT) and modified silane 3-amino-propyltriethoxysilane (APTS). Films were deposited on borosilicate glass substrates by a dip-coating technique. The refractive index, the thickness and the total attenuation coefficient of the waveguides were measured at 632.8 and 1550 nm by prism coupling technique. Starting from pure titania films, the addition of modified silane leads to a decrease in the refractive index and an increase in thickness. Squared electric field simulation has shown that the light confinement in the waveguide increases with the silane content of the so]. Emission spectra present a broad emission band due to the modified silane and EU emission transitions arising mainly from the D-5(0) level to the F-7(J) (J = 0-4) manifolds. The dependence of transition intensities and excited state lifetimes on the initial composition and also on the heat treatment performed was interpreted in terms of structural changes occurring during the preparation process. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Non-leachable highly luminescent ordered mesoporous SiO2 spherical particles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Phase Transformation in Titania Nanocrystals by the Oriented Attachment Mechanism: The Role of the pH Value

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

Sol-gel synthesis of mesoporous CaCu3Ti4O12 thin films and their gas sensing response

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nucleation and crystallization of titania nanoparticles in silica titania planar waveguides: A study by low frequency Raman scattering

SiO2 (1-x) - TiO2 (x) waveguides, with the mole fraction x in the range 0.07 - 0.20 and thickness of about 0.4 μm, were deposited on silica substrates by a dip-coating technique. The thermal treatments at 700-900°C, used to fully densify the xerogels, produce nucleation of TiO2 nanocrystals even for the lowest TiO2 content. The nucleation of TiO2 nanocrystals and their growth by thermal annealing up to 1300°C were studied by waveguide Raman spectroscopy, for the SiO2 (0.8) - TiO2 (0.2) composition. By increasing the annealing temperature, the Raman spectrum evolves from that typical of the silica-titania glass to that of anatase, but brookite phase is dominant at intermediate temperatures. In the low. frequency region (5-50 cm-1) of the Raman spectra, acoustic vibrations of the nanocrystals are observed. From the measured line shapes, we can deduce the size distribution of the particles. The results are compared with those obtained from the line widths in the X-ray diffraction patterns. Nanocrystals with a mean size in the range 4-20 nm are obtained, by thermal annealing in a corresponding range of 800-1300°C.

On the specific filtration mechanism of a mesoporous silica membrane, prepared with non-connecting parallel pores

We report the singular filtration properties of an ultrafiltration membrane made with mesoporous silica that exhibits cylindrical pores aligned mostly normal to the support. This membrane supported on tubular commercial macroporous alumina supports was prepared by the interfacial growth mechanism between stable silica-surfactant hybrid micelles made of the association of silica oligomers with polyethyleneoxide-based (PEO) surfactants and sodium fluoride, a well-known silica condensation catalyst [Boissière et al., An ultrafiltration membrane made with mesoporous MSU-X silica, Chem. Mater. 15 (2003) 460-463]. It appears that the combined effect of the silica nature of the membrane, whose surface charge can be easily adjusted by changing the pH and the non-connected cylindrical shape of the pores provides a new behavior in the retention properties, as proved by the filtration of polyoxyethylene polymers (PEO) with different molecular weights. Depending on the filtration conditions, a rejection rate of 80% and a steep cut-off at 2000 Da can be obtained or, on the reverse, polymers three times bigger than the pore diameter can diffuse through the membrane. This new filtration mechanism, which opens up new modes of separation modes, is explained in the light of both topology of the porous network and pH-dependent interactions between PEO polymers and silica porous media. © 2004 Elsevier B.V. All rights reserved.