Preparation of Silica-Gel Film with pH Indicators by the Sol–Gel Method

Gel films with various pH indicators were prepared by the sol–gel method without catalysts. The obtained gel films showed good response for various pH solutions as optical pH sensors and no leaching of the indicators was observed. The feature of absorption spectra of the indicators in the gel films was almost the same as that in the aqueous solutions. pKa of the indicators in the gel films was shifted with the increase of the TMOS content in the starting solutions. These results suggest that the pH indicators in the gel films were trapped in similar environment as in the solutions.     

Synthesis of Calcium Aluminate-Based Luminophores by the Citrate Nitrate Sol–Gel Process

Microwave-assisted sol–gel process was used to synthesize calcium aluminate and luminescent materials based on it, which find wide use in the manufacture of construction materials, catalysts, optical emission sources, and display devices. The major processes involved in the formation of crystalline calcium aluminate were identified resorting to powder X-ray diffraction, thermal analysis, scanning electron microscopy, and IR spectroscopy data. Synthetic steps have moderate activation energies in the 44–260 kJ/mol range. Luminescence characteristics of the obtained crystal phosphors were measured. The increase in the synthesis temperature to 1200°C and the increase in the activator concentration to 5 mol % enhance the luminescence of the Eu³⁺-activated calcium aluminate-based luminophore. Further increase in the concentration of the activator ions leads to luminescence quenching caused by the concentration effect.     

Vanadia-Silica Catalysts Prepared by Sol–Gel Method: Application for Epoxidation Reaction

Vanadia-silica xerogel and aerogel catalysts, with various V/Si molar ratios (0.05, 0.1, and 0.2), were prepared by sol–gel processing. Gels were obtained under acid catalysed conditions (HNO₃) from vanadium (III) acetylacetonate (V(acac)₃) and tetraethoxysilane (TEOS). Under these conditions, it was found that the gelation time increased with V/Si molar ratio. The structure and catalytic properties of the mixed oxides were found to be mainly influenced by the V/Si molar ratio and drying mode. The catalytic behaviour of the xerogels and aerogels was tested in the epoxidation reaction of trans-2-hexen-1-ol. The results showed that the V/Si molar ratio did not significantly influence the catalytic activity, although the effect of drying (xerogel vs. aerogel) was remarkable. Using a molar ratio TBHP/alcohol = 4/7, the epoxide yield was about 50% in the presence of xerogels, with ca. 8 h required to achieve stationary-conversion conditions in this heterogeneous-catalysis system. In contrast, the aerogel catalysts required only 2 h to reach stationary conversion conditions, due to partial leaching of the vanadium species from the solid and the associated contribution of a relatively rapid homogeneous catalysis mechanism to the overall conversion. These differences in catalytic behaviour were related to the vanadium speciation and the texture of the catalysts. To explore the origin of these differences, the catalysts were characterised by nitrogen physisorption, XPS, Raman spectroscopy, TGA/DTA and XRD.     

Encapsulation of β-Sitosterol in Polyurethane by Sol–Gel Electrospinning

Pristine β-sitosterol or in combination with other phytosterols is utilized in an array of enriched commercial foods. Considering the presence of β-sitosterol in different functional foods and its potential role in prevention and cure of neurodegenerative diseases, the aims of our investigation were to encapsulate β-sitosterol in nanofibers and to estimate influence of β-sitosterol on proliferation of fibroblasts. Electrospun nanofibers have widely been used as scaffolds to mimic natural extracellular matrix. Herein, our group for the first time establishes an innovative scaffold based on β-sitosterol and polyurethane using electrospinning. β-Sitosterol promotes epithelialization and possesses anti-oxidant and anti-inflammatory activities, whereas polyurethane, besides possessing biomedical uses, also enhances epithelial growth. We optimized the concentration (5%) of β-sitosterol in polyurethane to obtain homogenous solution, which can be spun without difficulty for the synthesis of β-sitosterol amalgamated scaffold. The resulted twisted nanofibers have been characterized via scanning electron microscopy and Fourier transform infrared spectroscopy. The viability of cells on twisted scaffold was examined using NIH 3T3 fibroblasts as model cell line. Incorporation of β-sitosterol in polyurethane changed the structure and size of nanofibers, and the twisted scaffolds were non-cytotoxic. Thus, the twisted nanoribbons, which contain anti-inflammatory β-sitosterol, can be utilized as a promising future material, which will help to ease inflammation and also aid in wound healing. In conclusion, the outcome of the preliminary research evidently points out the potential of twisted scaffold in biomedical applications.     

Passivation of Organic-Inorganic Hybrid Sol–Gel

A passivation method for improving long-term stability of organic-inorganic sol–gel material is reported. The effect is observed in experiments with two different passivation materials: Teflon AF and SiO₂. A regime of material curing prior to the passivation is found to strongly affect the optical loss. The degradation of waveguide loss with time due to moisture adsorption from the atmosphere is drastically suppressed by coating the material with a thin silica film. The results indicate a long-term optical loss below 0.3 dB/cm in coated waveguides, significantly smaller than that in uncoated waveguides. The mechanism of the loss reduction is described and experimentally confirmed.     

Photocatalytic Activity of Tio2 Nanostructures Formed by Sol–Gel Method in the Presence of Hydrofluoric Acid in the Transformation of Carbon Oxides

Theoretical and Experimental Chemistry - The photocatalytic activity of TiO2 nanostructures in the reduction of CO2 to CH4 and oxidation of CO to CO2 was studied. It depends significantly on the...     

Preparation of ZnFe2O4 Nanofibers by Sol‐Gel Related Electrospinning Method

Zinc ferrite gel fibers were prepared from the sol precursor by the electrospinning method, and the ZnFe₂O₄ polycrystalline nanofibers were obtained upon calcination of the gel fibers. The obtained ZnFe₂O₄ nanofibers composed of 20–30 nm nanocrystals were about one hundred to several hundred nanometers in diameter. The materials have been characterized by means of SEM, TEM, XRD, TGA, and IR techniques.     

Effect of Synthesis Parameters on Sol–Gel Silica Modified by Zirconia

An experimental strategy was developed to obtain mesoporous SiO₂-ZrO₂ mixed oxides via a sol–gel process, which involved the use of tetraethylorthosilicate (TEOS) and an inorganic Zr-containing salt. The effects of key process parameters on the properties of the materials were investigated, including the choice of Zr(IV) source (zirconium oxychloride or nitrate), the ZrO₂ content and the synthesis pressure (i.e. ambient pressure or hydrothermal conditions). The resulting solids were dried, calcined at 500 °C, and characterized by nitrogen physisorption, pyridine chemisorption, ²⁹Si Nuclear Magnetic Resonance and X-ray diffraction. The data revealed that mesoporous materials with very narrow pore diameter distribution were obtained when using the autoclave procedure from both zirconium nitrate and oxychloride salts. The surface areas and pore size distributions were a function of ZrO₂ content. Differences in acidity, as determined by pyridine adsorption, were observed depending on the synthesis parameters.     

Synthesis of VO2 Nanopowders. Part I. Sol–Gel Processing of Vanadium Alkoxide Precursor Within Inverse Micelles

Hydrolysis and condensation of VO(Oi–Pr)₃ within inverse micelles containing aqueous ammonia catalyst is conducted under different reaction conditions as a synthesis strategy for preparing VO₂ nanoparticles having average diameter <100 nm. Sol–gel processing of VO(Oi–Pr)₃ to form V_xO_y gel particles is controlled by varying NH₃(aq) concentration and using oleic acid or acetic acid pre-treatments. Isolated V_xO_y gel nanoparticles are reduced to VO₂ nanoparticles by thermal annealing, although annealing conditions must be optimized for each batch of gel particles. VO₂ nanoparticles of average diameters 24 or 70 nm prepared by this method show an expected hysteretic semiconductor-to-metal phase transition near 68 °C.     

Anti-Microbial Hydroxyapatite Particles Synthesized by a Sol–Gel Route

Sol–gel route was applied to synthesize anti-microbial hydroxyapatite (HAp) powders by the addition of silver 200–20000 ppm or zinc salts. The bacteria strain, Streptococcus mutans (S. mutans, ATCC 25175) was used in the anti-bacterial tests. HAp phase was reproducibly obtained by the preparation conditions: Ca(NO₃)₂-4H₂O and trietheyl phosphate as sources of calcium and phosphorus sources, respectively, and ethanol as the solvent, aging for 16 h at 80°C, gelation and drying at 80°C for 24 h, then calcining at above 350°C. TGA was used to analyze thermal properties of the as-prepared gel. XRD and FTIR were used to identify the crystalline phase and chemical structure. CaO appeared as an impurity after calcining above 650°C. In the solid-state anti-microbial tests on the brain heart infusion (BHI) agar plates, there formed a microbial inhibition zone surrounding the Ag/Zn added (greater than 2000 ppm) samples. In the liquid-state anti-microbial tests, S. mutans cells readily precipitated with pure HAp powders but not with Ag/Zn added (greater than 2000 ppm) HAp powders. The concentration of silver or zinc ions releasing from the Ag/Zn added HAp powders into the supernatant of the BHI broth was under detection limit of ICP-AES analyses. However, the growth of S. mutans reached same magnitude (6 × 10⁸ CFU/mL) whether pure HAp, 2000 ppm-Ag or 2000 ppm-Zn were added. Therefore, Ag/Zn added HAp powders developed in this research present microbial inhibition properties and are of potential as a solid-state anti-microbial agent.     

Polyaphrons as Templates for the Sol–Gel Synthesis of Macroporous Silica

Macroporous silica was synthesized using polyaphrons as shape-directing templates in a sol–gel hydrolysis scheme using tetraethyl orthosilicate (TEOS). Polyaphrons are a special class of high internal phase ratio emulsions (HIPRE) that can potentially be used in the continuous processing of long range ordered macroporous solids. The structures so formed were examined using a scanning electron microscope after thermal curing to 400C. The majority of the pores in the silica structures were in the range between 0.1 and 10 m. Key parameters affecting the polyaphrons template characteristics were varied and their effects on the final silica structure were studied.     

Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes

Homogeneous xSiO₂-(1−x)ZrO₂ coatings have been prepared onto glass-slides, monocrystalline Si and stainless steel (AISI 304) using sols prepared via acid and basic catalysis. Zirconium tetrabutoxide (TBOZr), zirconium n-propoxide (TPZ), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursors of zirconia and silica, respectively. The different parameters involved in the synthesis procedure, as molar ratios H₂O/alkoxides, NaOH/alkoxides, and sintering temperature have been analysed, correlating the stability and rheological properties of the sols. The evolution and structure of the sols and coatings have been studied by FTIR. Coatings have been prepared by dipping from acid and basic sols. Electrophoretic Deposition (EPD) technique has also been used to prepare coatings onto stainless steel from basic particulate sols in order to increase the critical thickness. A maximum thickness of 0.5 μ m was reached by both dipping and EPD process for 75SiO₂: 25 ZrO₂ composition. The critical thickness decreases with ZrO₂ amount depending strongly of the drying conditions. Si–O–Zr bonds have been identified by FTIR, indicating the existence of mixed network Si–O–Zr in the coatings obtained by the different routes. Crystallisation of ZrO₂(t) was only observed at high sintering temperature (900^∘C) by FTIR and confirmed by DRX.     

Enhancement of the Activity and Enantioselectivity of Lipase by Sol–Gel Encapsulation Immobilization onto β-cyclodextrin-Based Polymer

Candida rugosa lipase was encapsulated within a chemically inert sol–gel support prepared by polycondensation with tetraethoxysilane and octyltriethoxysilane in the presence of β-cyclodextrin-based polymer. The catalytic activity of the encapsulated lipases was evaluated both in the hydrolysis of p-nitrophenylpalmitate and the enantioselective hydrolysis of racemic Naproxen methyl ester. It has been observed that the percent activity yield of the encapsulated lipase was 65 U/g, which is 7.5 times higher than that of the covalently immobilized lipase. The β-cyclodextrin-based encapsulated lipases had higher conversion and enantioselectivity compared with covalently immobilized lipase. The study confirms an excellent enantioselectivity (E >300) for the encapsulated lipase with an enantiomeric excess value of 98% for S-naproxen.     

Synthesize and Characterization of Ca2CuO3 Nanostructures via a Modified Sol–Gel Method Assisted by Hydrothermal Process

A sol–gel-hydrothermal method was used to prepare the highly homogeneous nanopowder of Ca₂CuO₃ ceramic with an average diameter of about 20–30?nm. In comparison with the conventional sol–gel process, this method caused the more purity product with smaller size of particle due to a high pressure and long reaction time. Photoluminescence measurement indicated that for Ca₂CuO₃ nanoparticles there are two emission peaks: one sharp band at about 400?nm and one broad visible emission band. The band gap energy of Ca₂CuO₃ nanoparticles has been estimated to be 3.09?eV that is far above the values reported earlier. The results showed that the morphology and particle size of the synthesized samples can be obviously affected by the reaction temperature and molar ratio (w) between citric acid and calcium nitrate. In this procedure, diethylene glycol monobutyl ether was used as both the solvent and the modest surfactant.     

Preparation of Amorphous Silica-Alumina Using the Sol–Gel Method and its Reactivity for a Matrix in Catalytic Cracking

Amorphous silica-aluminas were prepared by the sol–gel method using organic templates such as carboxylic acid and the gel skeletal reinforcement method. Their reactivities as a matrix for the catalytic cracking were investigated. Malic acid (MA) was used as a catalyst for the sol–gel method, an organic template and a reagent for the dispersion of Al. When the ratio of MA/TEOS (tetraethoxysilane) increased from 0.22 to 1.22, surface area, pore volume and pore diameter increased and the mesopore was formed at 1.22. Their average BET pore diameters for 0.22 and 1.22 of MA/TEOS were 2.0 to 5.1 nm, respectively. Although conversions of n-dodecane were around 20% or less with single amorphous silica-aluminas, both single beta-zeolite and the mixed catalysts of zeolite and amorphous silica-aluminas showed much higher activity. Further, the mixed catalyst using silica-alumina with mesopore (MAT(MA122-5)) exhibited the higher ratio of multi-branched paraffin to single branched paraffin in the gasoline franction of products (C5–C11) than the mixed catalysts using silica-alumina with only micropore and silica with mesopore or single zeolite. In the gel skeletal reinforcement method, tetraethoxy orthosilicate (TEOS) was used as not only a precursor of silica but also an agent which reinforces the skeleton of silica-gel to prepare an aerogel and extremely large mesopores were formed for resultant silicas and silica-aluminas. When silica aerogel was reinforced by TEOS solution, the pore diameter and pore volume reached 30 nm and 3.1 cm³/g, respectively, in the N₂ adsorption measurement by the BJH method, indicating that most of pores for this silica consisted of mesopores. In catalytic clacking reaction of n-dodecane, the mixed catalyst prepared by beta-zeolite and silica-alumina with large mesopore exhibited not only the comparable activity to that for single zeolite but also the unique selectivity where large amounts of branched products were formed. When the catalyst beds of silica-alumina and zeolite were separated, the reference silica-alumina (ref.SA) → zeolite system exhibited the higher activity and the product selectivity close to those for MAT(ref.SA). It is likely that the primary cracking of n-dodecane on silica-alumina would occur to produce the primary cracked product which effectively reacted with zeolite and inhibited the coke formation by overcracking.     

Preparation of Zirconia Fibers via a Simple Aqueous Sol‐Gel Method

Polycrystalline tetragonal zirconia fiber was obtained by pyrolysis of precursor fibers from citrate‐acetate‐zirconium complex solution. The viscous zirconia sol with good spinnability was prepared by aging the starting solution of ZrOCl₂ · 8H₂O (ZOC) in the presence of acetic acid (HA) and citric acid (CA). The effects of molar ratio of zirconium cation to carboxylic acid and the aging time on the formation of spinnable sol were investigated. Thermogravimetric (TG) analysis, x‐ray diffraction (XRD), infrared (IR) spectra, and scanning electron microscope (SEM) techniques were used to characterize the sintered fibers. The results show that the fibers obtained at 1400°C are crack‐free with diameter of ca. 5–10 µm.     

Study of the Nano-Size Silica Sol–Gel Film as the Matrix of Chemically Modified Electrode

This paper reports a new method to make the sol–gel film from silicate. It provided more profitable conditions than hydrolysis of alkoxyl silane to prepare the high-quality nanometers thin film. The thin film could be applied as the matrix to directly modify the molecules of methylene blue on electrode surface and kept their electrochemical activity excellently. It exhibited the remarkable catalytic activity for the oxidation of NADH or reduction of hemoglobin while severally embedding them in the sol–gel film together with methylene blue.