Sol-gel coatings of BaO-TiO2-SiO2 compositions

New alkali resistant BaO-TiO₂-SiO₂ coatings have been developed via the sol-gel process. In the solutions and in the gels (T<300°C) an infrared absorption band at 930 cm^–1 gives the possible evidence of mixed Si-O-Ti bonds, which have not been found in the system SiO₂-TiO₂-ZrO₂. Baking the films at about 500°C for less than 1 h leads to stable layers with negligible residual carbon contents. Compositions near 20 BaO-40 TiO₂-40 SiO₂ showed the best performance.     

Kinetic study of zirconia crystallization from amorphous ZrO2-SiO2 composite precursors processed by sol-gel chemistry

Powder precursor gels with composition xZrO₂·(100–x)SiO₂, with selected values of x=8, 24, 43 and 75 mol%, were processed by sol-gel chemistry. Differential thermal analysis (DTA) was used to study crystallization in (cubic/tetragonal)-ZrO₂ during the heating of the reactive amorphous precursors. Kinetic parameters such as activation energy, Avrami's exponent and frequency factor have been simultaneously calculated from the computed DTA data using a previously reported kinetic model. The crystallization temperature decreases relative to the increase in the amount of ZrO₂, the value of the kinetic parameter of the crystallization being related to the value of x.     

Sol-Gel Preparation of Fast Proton-Conducting P2O5-SiO2 Glasses

We have investigated the proton conductivities of the sol-gel-derived P₂O₅-SiO₂ glass at –50 to 120°C. The obtained glass is porous, where the surface area, pore volume and pore diameter are 740 m²/g, 0.5 cm³/g and <5 nm, respectively. The freezing temperature of water molecules adsorbed in the pores was –20°C, which is much lower than that of free liquid water due to the quantum size effect of the water confined in the pores. The electrical conductivities followed the Arrhenius equation in the temperatures between –20 and 120°C. Below –20°C, the adsorbed-water molecules were frozen, resulting in a rapid decrease of the proton conductivity. Considering the high conductivity, chemical and thermal stability, this oxide glass membranes have potential for the fuel cell membrane.     

Effect of Zirconia Precursor on the Properties of ZrO2-SiO2 Sol-Gel Oxides

Sol-gel zirconia-silica oxides were synthesized with two zirconium precursors, zirconium n-butoxide and zirconium acetylacetonate, and two different hydrolysis catalysts, HCl and H₂SO₄. The samples prepared with HCl were additionally sulfated with a 1 M solution of H₂SO₄. Characterization was performed with FTIR and ²⁹Si-MAS-NMR spectroscopy, as well as with nitrogen adsorption. Because zirconium and silicon alkoxides have different hydrolysis rates, it was necessary to perform a pre-hydrolysis of the silicon alkoxide before mixing. The atom distribution in the ZrO₂-SiO₂ system depended on the zirconium precursor, which also determined the zirconium incorporation in the silica lattice, which was greater for zirconium acetylacetonate. The zirconium precursor also was responsible for the silanol concentration, which increases when samples were sulfated. Sulfating stabilizes the specific surface area. On sulfate samples calcined at 800°C BET areas larger than 500 m²/g were obtained.     

Preparation and Characterization of Amorphous ZrO2-SiO2 Composite Powders Processed by Sol-Gel Chemistry

Composite ZrO₂-SiO₂ powders, with different ZrO₂ contents, including pure ZrO₂ powders, were prepared by precipitation in SiO₂ suspensions, of zirconia gels from solutions of zirconyl chloride at pH = 11. These products were investigated in connection with the phase changes in ZrO₂ caused by heat-treatments. ZrO₂-SiO₂ mixtures containing 0–100% mol ZrO₂, were studied by differential thermal analysis (DTA), X-ray powder diffraction (XRD), temperature programmed desorption combined with mass spectroscopy (TPD-MS), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), to obtain information on the morphological and structural features of the particles before and during the heat treatment up to 1200°C. Specific surface areas were determined using nitrogen adsorption by the BET method. The results offer an explanation about some of the factors which can be influencing on the stabilization of metastable-cubic/tetragonal (C/T) phase of ZrO₂ and the evolution of surface areas (vulcano profile) observed in the composites.     

Kinetic study of surface nucleated MgO-CaO-Al2O3-SiO2 glasses

The paper investigated, by means of thermal analysis measurements, the validity of three different methods for the evaluation of the activation energy of crystallization for surface nucleated glasses belonging to the MgO-CaO-Al₂O₃-SiO₂ system, separating anorthite and diopside crystals. The values obtained from Kissinger equation of the activation energy for crystallization are comparable with those obtained by other authors for similar glassy systems, 90 to 150 kcal/mol. The results of the kinetic analysis using single-crystallization-peak method should be corrected taking into account the dimensionality of crystal growth.The authors thank the M.U.R.S.T. for financial support.     

Structure of TiO2 in TiO2-SiO2 prepared by a complexing agent-assisted sol-gel procedure

Many types of TiO₂-SiO₂ (Ti:Si=50:50 mol%) were prepared by the sol-gel procedure with and without 2-methyl-2, 4-pentanediol (MPD) as an organic ligand. The effect of MPD on the gel structure and the properties of the TiO₂ crystals were studied by XRD and raman spectroscopy, and the effect of the sol standing time on the properties of the TiO₂ crystals were also studied by XRD spectroscopy. In the gels with MPD, anatase of TiO₂ appeared at approximately 580°C, and the crystal structures were similar despite the difference in the gel preparation procedure. The titania gels with MPD were presumed to be dispersed in the silica gel matrix without any Ti-O-Si bond. In the presence of MPD, the formation of titania gels is controlled and the specified TiO₂ crystal is produced.     

H2SO4-SiO2: Highly Efficient and Reusable Catalyst for per-O-Acetylation of Carbohydrates Under Solvent-Free Conditions

Sulfuric acid immobilized on silica gel (H₂SO₄-SiO₂) was used as an efficient promoter for per-O-acetylation of carbohydrates with acetic anhydride under solvent-free conditions. The substrates include not only monosaccharides and disaccharides, but also glycosides. The catalyst is recyclable and stable at room temperature, and the reaction protocol is simple, is cost-effective, and gives good isolated yield with high purity. The large-scale reactions also proceeded conveniently and in high yields.     

Preliminary Study on the Effect of pH on Thermal Transformation of Some Diphasic Al2O3-SiO2 Gels

Diphasic Al₂O₃-SiO₂ gels have been synthesized by hydrolyzing ethyl orthosilicate at three different pH ranges in presence of colloidal boehmite. Result shows that dominant mullitization process are sensitive to pH of the gelation process. At highly acidic pH range, solid state reaction between corundum and cristobalite occurs, and develops liquid phase for mullite nucleation. At moderately acidic pH, nucleation and crystallization are most operative for nucleation in aluminosilicate matrix. In highly basic pH region, Al-Si spinel phase develops by incorporation of Si in aluminous phase as intermediary phase. Polymorphic transformation of it may be the cause of sudden mullitization. The changes in crystallization sequence in three distinct processes may be due to variation in the nature and size of silicic acid particle formed by hydrolysis and condensation of TEOS at different pH.     

Application of Hot Press Sintering to Na2O-B2O3-SiO2 Gels Containing Quantum Dots for Lowering of Densification Temperature

Na₂O-B₂O₃-SiO₂ (NBS) gels containing a large amount of CdS quantum-dots (10 wt%) were densified using the hot press (HP) sintering method. By HP treatment, full-densification temperature could be lowered by about 40°C than that of the normal non-pressing (NP) heat treatment. Exciton absorption of CdS quantum-dots in HP-sample showed a large blue shift compared with that in the NP sample, and the size-distribution of CdS dots remained very sharp, with a mean particle diameter d = 3.66 nm and a standard deviation of = 0.72. HP pressure had a large effect on the reduction of sintering temperature and time, resulting in the suppression of the aggregation and growth of CdS quantum-dots in NBS glasses.     

Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones Using Ce(SO4)2-SiO2 as a Heterogeneous and Recyclable Catalyst

A simple and efficient synthesis of 3,4-dihydropyrimidinones or thiones is described, using silica-supported ceric sulfate [Ce(SO₄)₂-SiO₂] as a heterogeneous catalyst from an aldehyde, 1,3-dicarbonyl compound, and urea or thiourea at 110 °C under solvent-free conditions. Compared with the classical Biginelli reaction, this new method consistently has better yields, short reaction time, easy separation, and tolerance toward various functional groups.     

Formation of Anatase Nanocrystals in Sol-Gel Derived TiO2-SiO2 Thin Films with Hot Water Treatment

We have successfully prepared transparent and porous anatase nanocrystals-dispersed films by treating the sol-gel derived TiO₂-SiO₂ films containing poly(ethylene glycol), PEG, with hot water. This process was done at temperatures lower than 100°C under atmospheric pressure, and thus anatase nanocrystals-dispersed films can be formed on various kinds of substrates including organic polymers with poor heat resistance. The changes in structure and composition of the TiO₂-SiO₂ gel films with hot water treatment were related to the formation process of anatase nanocrystals in the TiO₂-SiO₂ gel films with hot water treatment. The formation of anatase nanocrystals was found to proceed to hydrolysis of Si–O–Ti bonds and dissolution of SiO₂ component. In addition, porous film structure formed by leaching of PEG with hot water treatment led to homogenous dispersion of anatase nonocrystals in the films.     

Silica-Supported Ferric Chloride (FeCl3-SiO2): An Efficient and Recyclable Heterogeneous Catalyst for the Preparation of Arylaminotetrazoles

An efficient method for preparation of 5-arylamino-1H-tetrazole and 1-aryl-5-amino-1H-tetrazole derivatives is reported using FeCl₃-SiO₂ as an effective heterogeneous catalyst. Generally, when the substituent in arylcyanamide is a strongly electron-withdrawing group, the position of the equilibrium would shift toward 5-arylamino-1H-tetrazole, whereas with an electron-releasing substituent, the position of the equilibrium would shift toward 1-aryl-5-amino-1H-tetrazole.     

Use of Nb(2)O(5)-SiO(2) in an automated on-line preconcentration system for determination of copper and cadmium by FAAS

A procedure for the determination of trace level of copper(II) and cadmium(II) by FAAS using an on-line preconcentration system has been proposed. In this system, copper and cadmium ions were adsorbed onto a minicolumn packed with silica gel modified with niobium(V) oxide (Nb₂O₅-SiO₂), followed by nitric acid elution in reverse mode and determination on-line by flame atomic absorption spectrometry (AAS) without interference of the matrix. Chemical and flow variables as well as concomitant ions were studied in the developed procedure. The enrichment factor for copper(II) and cadmium(II) was 34.2 and 33.0, respectively, using a preconcentration time of 2 min. The limit of detection for copper(II) and cadmium(II) was 0.4, and 0.1 μg l⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation in solutions containing 15 μg l⁻¹ of copper and 10 μg l⁻¹ of cadmium, by analyzing a series of seven replicates, was 1.8 and 1.6%, respectively. The accuracy was assessed through recovery experiments of certified material and water samples.     

Sol-Gel Derived TiO2-SiO2 Fibres

TiO₂−SiO₂ fibres with 0, 5, 10 and 20 volume % SiO₂ have been prepared by drawing from a gel followed by sintering at different temperatures. Nearly one meter long fibres can be drawn easily in conditions of about 50% relative humidity. Addition of SiO₂ inhibits the crystallisation of TiO₂ and also the anatase → rutile transformation and improves the strength of the fibres. While the pure TiO₂ fibres are brittle, those with 5, 10 and 20 volume % SiO₂ are flexible and strong. Tensile strength values as high as 3 GPa have been achieved in the 10 volume % SiO₂−TiO₂ fibres. Fibres heated above 900°C are brittle. The shape of the cross section of the fibres is found to depend on their diameters.     

Efficient and Convenient Protocol for the Synthesis of 3,5-Disubstituted 1,2,4-Oxadiazoles Using HClO4-SiO2 as a Heterogeneous Recyclable Catalyst

Silica-supported perchloric acid (HClO₄-SiO₂) was found to be a new, highly efficient, inexpensive, and reusable catalyst for a rapid and efficient synthesis of various 1,2,4-oxadiazoles with good to excellent yields under solvent-free conditions. The present methodology has been effectively utilized for the synthesis of oxolamine, an anti-inflammatory drug.     

三元杂化TiO2-SiO2-POMs催化剂的合成及其在可见光降解罗丹明B中的应用

采用分步溶胶-凝胶法制备的三元杂化催化剂TiO₂-SiO₂-杂多酸(POMs)在可见光降解工业染料罗丹明B中表现出了高效反应活性. 利用时间分辨微波传导(TRMC)和漫反射光谱(DRS)研究了催化剂在可见光区的光催化性能, 实验结果表明: 在三元杂化催化剂内, 二氧化钛和二氧化硅的键合加强了催化剂在可见光区的响应和吸收, 二氧化钛和杂多酸的结合提高了反应活性位(空穴-电子对)的稳定性. 三元杂化催化剂TiO₂-SiO₂-POMs中组分之间的协同效应促进了可见光光催化性能的提高.     

Synthesis of Gels in the System Na2O-ZrO2-SiO2

Gels have been synthesized in the SiO₂-Na₂O-ZrO₂ system and calcined at various temperatures up to 700°C. They have been studied by infrared absorption spectroscopy. The position of the asymmetric stretching frequency of the SiO₄ unit is used as a tracer of the homogeneity. It is shown that sodium increases the solubility of zirconium in the silica matrix as already observed in fused glasses.     

Structural analysis of SiO2 gel films by high energy electron diffraction

The structure of SiO₂ gel-films prepared from acid and basic TEOS solutions is analyzed by high energy transmission electron diffraction method. The Si-O bond length of gel-films is 1.58 to 1.60 Å, which is shorter than that of vitreous silica (1.61 Å) but similar to that of 80 Å thick evaporated a-SiO₂ film. An atomic pair peak with 0.81 Å distance exists on the reduced radial distribution functions of the gel-films, which is believed to be O-H, but being smaller than that of H₂O (0.969 Å).     

Fluoroboric acid adsorbed on silica gel catalyzed regioselective ring opening of epoxides with nitrogen heterocycles

Aryl epoxides can be opened in a regioselective and efficient manner with nitrogen heterocycles such as indoles, pyrroles and imidazoles in the presence of a catalytic amount of HBF₄-SiO₂ under mild conditions to afford the corresponding C-alkylated derivatives in good yields and with a high regioselectivity.