About the synthesis and thermal stability of SiO2-aerogel

Aerogels are extremely porous high-tech materials based on inorganic oxides, especially silica. The paper describes synthesis and properties of SiO₂-aerogel, and changes occurring during heating of SiO₂-aerogel in the temperature range from 20 to 1000°C. Four thermoanalytical methods were used: Thermodilatometry, Differential thermal analysis, Thermogravimetry and Derivative thermogravimetry.     

SiO2 Xerogel: A Suitable Inert Support for Microbial Growth

A silica xerogel was prepared at pH 2 by the hydrolysis-condensation reactions of the sol-gel method. Silica xerogel was used as a support for the growth of two filamentous fungi: Aspergillus niger ATCC 9642 and Phanerochaete chrysosporium A594. In both cases, an apparent abundant mycelia growth (5.5 mg biomass/g dry xerogel and 4.7 mg biomass/g dry xerogel respectively) was observed. A phase of rapid consumption of glucose which lasted until 96 h of culture with sugar consumption rate of 0.075 mg sugar/g support h and 0.042 mg sugar/g support h respectively, was also observed. Scanning electron microscopy (SEM) showed a superficial colonisation of both strains even in the occasional imperfections and crevices of the xerogel. This novel application of sol-gel metallic oxide systems suggests the potential use of an inert and versatile support which could be valuable, for example for solid state fermentation fundamental studies.     

Preparation and characterization of CuO/SiO2 and NiO/SiO2 with bimodal pore structure by sol-gel method

CuO/SiO₂ and NiO/SiO₂ with bimodal pore structure were prepared by sol-gel reactions of Tetra-methoxysilane (TMOS) and the respective metal nitrate in the presence of poly (ethylene oxide) (PEO) with an average molecular weight of 10 000 and the catalyst of acetic acid. In this process, the interconnected macroporous morphology was formed when transitional structures of spinodal decomposition were frozen by the sol-gel transition of silica. The addition of copper and nickel into the silica-PEO system had a negligible effect on the morphology formation. In gel formation, it was found that NiO crystalline sizes in the samples increased with decreasing Si/Ni molar ratio. It was considered that PEO interacted with both silica and nickel cations. In the CuO/SiO₂ with the presence of PEO_, CuO crystalline sizes were larger than those of NiO/SiO_2. It was considered that there was no obvious interaction between the Cu cation and PEO, most of the copper ions in wet silica gel were present in the outer solution. They easily aggregated as copper salts in the drying process of wet gel and decomposed into CuO particles in heating. While in the CuO/SiO₂ with the absence of PEO, the Cu was selectively entrapped as small particles in the gel skeleton due to the interaction between Cu aqua complex and silica gel network.     

Preparation and Evaluation of Octadecyl-Bonded ZrO2/SiO2

ZrO₂/SiO₂ particles, which were prepared by a layer-by-layer self-assemble technique and consist of micrometer-sized silica spheres as cores and nanometer-sized zirconia particles as surface coatings, have a higher surface area and pore volume than other zirconia supports have. Further more it is more stable than silica is. In this paper we made a reversed-phase support by bonding octadecyltrichlorosilane on ZrO₂/SiO₂ particles, it had a comparable high carbon amount of 9.62% and good chemical stability being stable up to pH 11. The chromatographic behavior showed that the support acted as a true reversed chromatographic stationary phase and had a hydrophobic selectivity. Basic and aromatic compounds are well separated and the peaks are symmetrical.     

SiO2-TiO2 membranes by the sol-gel process

The use of membranes for gas separation represents an important alternative from the viewpoint of energy conservation in industrial separation processes. Polymeric Si-Ti sols prepared from titanium isopropoxide (Ti(OPrⁱ)₄) and tetraethoxysilane (TEOS) were used to deposit membranes on α-Al₂O₃ supports. Acetylacetone (2,4 pentanedione, acacH) and isoeugenol (2-methoxy-4-propenylphenol, isoH) were employed separately to chelate the Ti precursor in order to slow down the chemical reactivity, avoiding precipitation. The radial distribution functions (RDF) of the gels aging at room temperature were obtained. The xerogels were studied by Thermal Gravimetric (TGA) and Differential Thermal (DTA) Analysis in air. The Microporosity of the solids calcined at 773 K was determined by N₂-adsorption at 77 K. The membrane thickness was determined from SEM photographs. Preliminary permeance results of the supported membranes on commercial alumina support were obtained for He, N₂ and CO₂ in a single gas equipment. At 773 K the separation factors α(He/CO₂) and α(N₂/CO₂) for both membranes exceeds the theoretical Knudsen limit.     

Preparation of Cu/SiO2 Catalyst by Solution Exchange of Wet Silica Gel

Structural formation process of Ni/SiO₂ and Cu/SiO₂ catalysts prepared by solution exchange of wet silica gel was investigated. Microstructures of Cu/SiO₂ and Ni/SiO₂ were quite different from each other. In the case of Cu/SiO₂, Cu particles with diameter of ca. 3–5 nm dispersed homogeneously at less Cu content, and the particle size of Cu as well as pore size of silica gel support increased with increasing Cu content. In the Ni/SiO₂, the Ni particles with diameter of ca. 6–10 nm gathered densely to form aggregates in silica matrix resulting in sea-island structure, whereas the size of Ni particle slightly increased with increasing Ni content. The difference in the structure of the metal-silica composites is probably caused by the difference in interaction between silica gel network and metal ions during drying and heating processes.     

Microporous SiO2 and SiO2/MOx (M=Ti,Zr, Al) for ceramic membrane applications: A microstructural study of the sol-stage and the consolidated state

Microporous SiO₂ and SiO₂/MO₂ (M=Ti, Zr, Al; 10 mol% MO_x) materials for gas separation membrane applications have been prepared from polymeric sols. Characterization of these sols with SAXS showed that the mean fractal dimension of the SiO₂ sols is 1.3–1.4 with a radius of gyration of approximately 2.5 nm. The dried and calcined films are microporous and the pore size distribution was bimodal with maxima at diameters of 0.5 nm and 0.75 nm. For the SiO₂/TiO₂, SiO₂/ZrO₂ and SiO₂/Al₂O₃ systems, much milder reaction conditions proved to be necessary to obtain sols with comparable fractal dimensions due to the high reactivity of the Ti/Zr/Al-alkoxides. Microporous supported membranes with molecular sieve-like gas transport properties can be prepared from a relatively wide range of sol structures: from polymers too small to characterize with SAXS to structures with fractal dimensions: 1<d _f<2.04.     

Proton Affinity at the Porous Surface of SiO2-TiO2 Binary Oxides

SiO₂-TiO₂ binary oxides are typically used as solid supports for different applications, from catalysts to optics. Tailoring the pore diameter, pore size distribution, and surface area is of great importance for any of those applications. Tailoring the chemical properties of the porous surface, e.g. in terms of polarity or acidity, is of capital importance as well. Thus, in catalytic applications or in sensing devices, where diffusion of a solute through the matrix is required, the affinity/compatibility of the solute with the matrix porous surface will determine the proper work of the device. Moreover, when the sensor is based on the adsorption of an active organic molecule or biomolecule on the porous surface matrix, the proton concentration at the surface may also modify the behavior of the active molecule. In this work, the proton affinity of the porous surface is tailored by the preparation of number of SiO₂-TiO₂ binary oxides with different SiO₂/TiO₂ weight ratios. Proton affinity is studied through the incorporation of a pH indicator as bromocresol green.     

Hybrid Inorganic-Organic Sol–Gel Coatings in the SiO2-TiO2 System

In the present work, the influence of substituted Si-alkoxides on the structural and optical properties of films obtained in the SiO₂-TiO₂ system was studied. Methyltriethoxysilane (MTEOS) and 3-(tri-methoxysilyl)propyl methacrylate (TSPM) were used as SiO₂ sources and Ti(OBu)₄ was used as TiO₂ source. Acetylacetone was added to the Ti(OBu)₄ as chelating agent and the synthesis was carried out in acid medium. The films were deposited on oxidized Si-wafers by spin-coating. The films were characterized by XRD, spectro-ellipsometry (SE), and atomic force microscopy (AFM). The results obtained have shown that in the case of hybrid films the desired thickness could be obtained in a single deposition step. The thickness of the films and the optical properties are controlled by the bulkiness of the organic substitute bounded to Si. Among other optical applications, the potential use of such films as optical waveguides is proposed.     

Size dependence of SiO2 particles enhanced glucose biosensor

A wide size range of SiO₂ particles were synthesized and were used as enzyme immobilization carriers to fabricate glucose biosensors. The size of the particles was in the range of 17-520 nm. These biosensors could be operated under physiological conditions (0.1 M phosphate buffer, pH 7.2). Particle size could affect the performance of SiO₂ modified glucose biosensors drastically. The smaller particles had higher performance. The smallest SiO₂ modified biosensor could work well in the glucose concentration range of 0.02-10 mM with a correlation coefficient of 0.9993. Its sensitivity was 2.08 μA/mM and the detection limit was 1.5 μM glucose.     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.     

Low-Density Forsterite (Mg2SiO4) Powders Prepared from Modified Alkoxides

2MgO-SiO₂ low-density powders have been prepared from alkoxide precursors modified with acetic anhydride. The resultant solutions did not gel, but formed precipitates. These consisted of an organic magnesium compound and amorphous silica. Tapping densities comparable with those of forsterite aerogels were obtained, with the density increasing as the precursor solution concentration increased. Crystalline forsterite formed around 790°C. Higher initial solution concentrations led to greater amounts of MgO in the powders after heating to 1000°C. Transmission electron microscopy showed primary particles between 20 and 30 nm which formed loose fractal agglomerates. By altering the preparation conditions, powders with morphologies more like aerogels than xerogels could be produced.     

Calcination of SiO2-aerogel in Oxidizing Atmosphere

Differences in mass loss occurring in the course of dynamic and isothermal heating of SiO₂-aerogel and changes of specific surface and hydrophylicity during calcination were studied by thermal analysis. SiO₂-aerogel was prepared from tetramethoxysilane (TMOS) hydrolyzed by ammonia solution at 0°C with molar ratio TMOS: H₂O:NH₄OH 4:1:0.01. Differences are caused mainly by oxidation of organic matter and by diffusion of products of the oxidation. Heat transfer has none or little effect on the differences. Samples calcined at temperatures about 300°C reach maximum hydrophilicity though they still contain small amounts of residual organic matter. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electrochemical behaviour of SiO2 sol-gel coatings on stainless steel

SiO₂ coatings onto stainless steel substrates have been prepared by sol-gel in order to study the performance and mechanism of attack in different corrosive solutions. The electrochemical behaviour of the samples has been evaluated by Electrochemical Impedance Spectroscopy using NaCl and HCl as electrolytes. Comparative tests have been performed on samples with one and two silica layers as well as on uncoated ones. SiO₂ coatings produce no important protection of stainless steels subjected to electrochemical corrosion. This behaviour may be explained by micropores and microcracks produced during the coating sintering.     

Synthesis of SiO2-TiO2 xerogels by sol-gel process

A new method to synthesize SiO₂-TiO₂ gels by sol-gel process has been developed. This technique uses tetraisopropylorthotitanate [Ti(O ⁱ Pr)₄] and tetraethylorthosilicate [TEOS]: they are mixed in the same solvent and then directly hydrolysed. This one-step reaction is possible because of the use of 2-methoxyethanol, a protic polar solvent. This alcohol plays two different specific roles: it acts as a solvent as well as a stabilizer of titanium alkoxide towards the hydrolysis-precipitation reaction. So, by an accurate adjustment of the quantity of methoxyethanol in the mixture, we can control the reactivity of the titanium precursor.Monolithic and transparent xerogels were obtained whatever the composition. Three monolithic SiO₂-TiO₂ gels containing 20, 50 and 75 mol% of TiO₂ were prepared and studied in details.By using the TG-DSC analysis, we can follow the evolution of the loss of water and organic residues.The structural evolution of gels during calcination is characterized by IR spectroscopy and X-Ray diffraction.     

Rh Inclusion in Sol-Gel SiO2. Effects of Rh Precursors on Metal Dispersion and SiO2-Rh Thermal Behavior

RhCl₃·nH₂O and [RhCl(C₂H₄)₂]₂ are used as precursors for the preparation of 1%Rh in sol-gel derived SiO₂. The gelling process of Si(OEt)₄ is carried out in the absence of solvent and under strong acid catalysis. The thermal behavior of Rh precursors, of SiO₂ gel and Rh-SiO₂ composites is independently studied by analysing organic species released at definite temperature intervals and concomitantly collecting infrared, XPS, TEM, XRD and porosity data. Results indicate that nanometric Rh particles may be obtained from [RhCl(C₂H₄)₂]₂, their dispersion being homogeneous, dense and stable up to 250°C, whereas RhCl₃·nH₂O affords less metallic dispersion with other crystalline Rh-species; in both cases, well-shaped Rh metal crystallites are obtained at 650°C. The different synthetic approaches used for the preparation of RhCl₃- and [RhCl(C₂H₄)₂]₂-derived samples, are invoked to account for the features of Rh dispersion obtained by mild temperature treatment. Moreover, the particular procedures for sol-gel SiO₂ synthesis are related to the high-temperature maintenance of great porosity and elevated specific surface area.     

SiO2-Iron Oxide Composites Obtained by Sol-Gel Method

Composite SiO₂-iron oxide materials were prepared by three experimental procedures. In the first case (1), the iron oxides were precipitated during the sol-gel process. In the second case (2), the SiO₂ matrix was initially obtained, and the iron oxides were formed by thermal treatment after impregnation of a soluble Fe²⁺ salt in the previously processed matrix. In the third method (3), ferrite powders, prepared by wet chemical method, were embedded into a SiO₂ based sol-gel matrix. Two type of precursors (tetraethoxysilane (TEOS) or methyltriethoxysilane (MTEOS) were used as SiO₂ sources. Various properties versus both type of precursor and on the method of preparation were noticed. Materials with high porosity and nano-sized iron oxide content could be prepared using the mentioned above methods.     

Preparation of ethyl levulinate from wheat stalk over Zr(SO4)2/SiO2

A series of Zr(SO₄)₂/SiO₂ solid acid catalysts with different Zr(SO₄)₂ loadings were prepared by water-soluble-impregnation method at room temperature. Then, the prepared catalysts were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectrum, X-ray diffraction, adsorption/desorption of N₂, and temperature-programmed desorption of NH₃. The results showed that the active component Zr(SO₄)₂ was successfully adhered to the mesoporous SiO₂, and the acid amount of Zr(SO₄)₂/SiO₂ increased with the increasing of the Zr(SO₄)₂ loadings. Finally, the wheat stalk was used as raw material and depolymerized over Zr(SO₄)₂/SiO₂ to produce ethyl levulinate (EL). The reaction mixture was separated and purified by filtration and vacuum distillation. The kinetic characteristics and the reaction pathway were also studied. A comparative study showed that 20 wt.% Zr(SO₄)₂/SiO₂ exhibited higher catalytic activity. When reaction temperature, time, catalyst dosage and Zr(SO₄)₂ loadings were 190 °C, 50 min, 20 wt.% and 30 wt.%, the EL yield reached a maximum of 17.14%. The relative content of EL exceeded 90% after three steps of distillation.     

Devitrification Behavior of Calcium Phosphate Glasses Containing Al2O3 and SiO2 Additives

The effects of Al₂O₃ and SiO₂ additives on the crystallization of calcium phosphate glasses were studied. When the Al₂O₃ content was higher than 7 mol%, surface devitrification occurred in the glasses. However, for glasses with Al₂O₃ contents higher than 10 mol%, bulk devitrification predominanted. For the glasses with SiO₂, a surface devitrification mechanism predominanted. Non-isothermal DTA techniques were applied in order to establish the devitrification mechanism, and the kinetic parameters of crystal growth were obtained. The parameter m depends on the mechanism and morphology of devitrification of calcium phosphate, glass containing SiO₂ as additive, the values of m being lower than 1.2. These results indicate that the devitrification is controlled by the reaction at the glass-crystal interface, or occurs from surface nuclei. This revised version was published online in July 2006 with corrections to the Cover Date.     

An Efficient Procedure for the Synthesis of Benzoxazole and Benzothiazole Derivatives Using a H2O2/SiO2-FeCl3 System

A series of benzoxazole and benzothiazoles was readily prepared from the reaction of ortho-aminophenol/ortho-aminothiophenol and aldehydes using solid silica supported ferric chloride (SiO₂-FeCl₃) as catalyst followed by oxidation with H₂O₂ under ambient conditions. Some of advantages of this method are a simple and convenient procedure, easy purification, and shorter reaction times.

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