Photoelectrochemical Properties of Sol-Gel Processed Ag-TiO2 Nanocomposite Thin Films

Ag-TiO₂ thin films were prepared with a sol-gel route, using titanium isopropoxide and silver nitrate as precursors, at 0, 0.03 and 0.06 Ag/Ti nominal atomic ratios. After drying at 80°C, the films were fired at 300°C, 500°C, and 600°C for 30 min and 5 h. Glancing angle X-ray diffraction (XRD) analysis and X-ray photoelectron spectroscopy (XPS), with depth profiling of the concentration, were used to study the films. XPS analysis showed the presence of C and N as impurities in the nanocomposite films. Their concentration decreased with increasing the firing temperature. Chemical state analysis showed that Ag was present in metallic state, except for the outer layer where it was present as Ag⁺. For the films prepared with a Agt/Ti concentration of 0.06, depth profiling measurements of the film fired at 300°C showed a strong Ag enrichment at the outer surface, while composition remained almost constant within the rest of the film, at Ag/Ti atomic ratio of 0.02. Two layers were found for the films heated to 500°C, where the Ag/Ti ratios were 0.015 near the surface and 0.03 near the substrate. The photoelectrochemical properties of Ag-TiO₂ were studied for thin films deposited on ITO substrates. Photocurrents of Ag-TiO₂ nanocomposite electrodes fired at 300°C were observed even at visible light, for wavelengths longer than 400 nm.     

Synthesis, characterization, and photocatalytic activity for hydrogen evolution of nanocrystalline mesoporous titania prepared by surfactant-assisted templating sol-gel process

Nanocrystalline mesoporous titania was synthesized via a combined sol-gel process with surfactant-assisted templating method, treated under various calcination conditions, and evaluated for its photocatalytic activity through photocatalytic hydrogen evolution from an aqueous methanol solution. In this synthetic method, applied surfactant template molecules functioned as both mesopore-forming and gelation-assisting agents. The resulting products were methodically characterized by TG-DTA, XRD, N₂ adsorption-desorption, diffuse reflectance UV-Vis spectra, SEM, and TEM analyses. The partial phase transformation from anatase to rutile occurred beyond calcination temperature of 600 °C and anatase-rutile transition kinetics was also investigated. The calcination conditions and crystalline phases existing in the products exerted significant effect on the photocatalytic hydrogen evolution activity. The activity of the synthesized titania treated under appropriate calcination conditions was considerably higher than that of commercial titania powders, Ishihara ST-01 and Degussa P-25. It is clearly seen that the introduction of mesopore into titania photocatalyst substantially improved the photocatalytic performance.     

Sol-Gel Preparation and Characterization of Ag-TiO2 Nanocomposite Thin Films

Ag-TiO₂ thin films were prepared with a sol-gel route, using titanium isopropoxide and silver nitrate as precursors, at 0.03 and 0.06 Ag/Ti nominal atomic ratios. After drying at 80°C, the films were fired at 300°C and 500°C for 30 min. The films were analysed by X-ray diffraction (XRD) with glancing angle, and X-ray photoelectron spectroscopy (XPS), with depth profiling of the concentration. XPS analysis showed the presence of C and N as impurities in the nanocomposite films. Their concentration decreased with increasing the firing temperature. Chemical state analysis showed that Ag was present in metallic state, except for the very outer layer where it was present as Ag⁺. For the films prepared with a Ag/Ti concentration of 0.06, depth profiling measurements of the film fired at 300°C showed a strong Ag enrichment at the outer surface, while composition remained almost constant within the rest of the film, at 0.019. For the films heated to 500°C, two layers were found, where the Ag/Ti ratios were 0.015 near the surface and 0.026 near the substrate.     

Use of bomb calorimetry to assess recovery of waste industrial mineral oils through regeneration

Emanation thermal analysis (ETA), based on the measurement of the release of radon previously incorporated into the sample, was used to characterize the differences in the thermal behavior porous titania film (thickness 200 nm),when heated in argon and in oxygen, respectively, in the range from 20 to 800°C. It was observed that the annealing of porosity and structure defects in the near surface layers of the porous titania film (anatase) was enhanced on heating in oxygen in comparison to the heating in argon. ETA results were compared with SEM micrographs and XRD patterns of the titania film samples heated to 500 and 800°C, respectively. A mathematical model was used for the evaluation of the temperature dependence of the titania films microstructure development.This revised version was published online in November 2005 with corrections to the Cover Date.     

Sol-Gel Nanosized Semiconducting Titania-Based Powders for Thick-Film Gas Sensors

Pure, 5 at%, and 10 at% Ta- or Nb-doped TiO₂ nanosized powders were prepared by the sol-gel method. The powders heated to 400°C have the crystalline anatase structure. While the pure TiO₂ powder heated to 850°C has the rutile structure, the addition of Ta and Nb inhibited the anatase-to-rutile phase transformation at this temperature. Ta was soluble in the titania lattice up to the concentration of 10 at%, while the solubility of Nb was 5 at%. Thick films were fabricated with these powders by screen printing technology and then fired at 650°C and 850°C for 1 h. SEM observations showed that the anatase-to-rutile phase transformation induces a grain growth of about one order of magnitude for pure TiO₂. The addition of Ta and Nb is effective to keep the TiO₂ grain size at the nanometric level even at 850°C. Conductance measurements showed that a good gas response is observed only for the nanostructured titania-based films. The CO response of these materials is only slightly affected by humidity.     

Bioactive Ca10(PO4)6(OH)2−TiO2 composite coating prepared by sol-gel process

The sol-gel prepared titania (TiO₂) has recently been demonstrated with a promising bioactivity [1]. It forms a chemical bond with the living bone in the body, although the bonding is not very strong. The present study is intended to improve the bone-bonding ability of the titania gel. The goal is achieved by impregnating the titania with hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂). The processing route includes the following steps: (1) the titania sol solution was prepared; (2) the solution was mixed with fine hydroxyapatite (HA) powders; (3) the mixture was used to produce a coating on a commercial pure titanium (c.p. Ti) or Ti6A14V plate by a dip coating technique; (4) the coating was fired at 400–600°C. The resulting coating is a composite consisting of hydroxyapatite embedded in the matrix of the titania gel. Such HA-TiO₂ composite coating is capable of inducing the hydroxyapatite precipitation from a simulated body fluid. When implanted in femurs of goat, the composite coating shows a bonding with bone. Its bone-bonding strength is twice as high as that of the pure titania gel coating. The results indicate that impregnating with hydroxyapatite is a promising way to increase the bioactivity of the titania gel.     

Surface Area Study of High Area Cobalt Aluminate Particles Prepared by the Sol-Gel Method

Cobalt aluminate particles were prepared by the sol-gel method, starting from aluminum sec-butoxide and cobalt salts with a Co:Al ratio of 1:3. Samples with the same composition were also prepared by the citrate-gel method from cobalt and aluminum nitrates and citric acid. The particles were calcined to temperatures between 400 and 1000°C, for the formation of the mixed oxide having spinel structure. The surface properties of the different samples (BET surface area and pore size distribution) were measured. The highest BET surface area obtained (about 339 m²/g) corresponds to a sample prepared by cobalt acetate and aluminum sec-butoxide, calcined at 400°C. The surface area of the sample is reduced progressively as the sample is calcined to higher temperatures (to about 65 m²/g at 1000°C). Narrow pore size distributions were observed with average pore radius ranging from 17–20 Å, for samples heated to 400°C, to about 55–65 Å, for samples heated to 1000°C. The different surface areas and porosities obtained for particles prepared by different methods, different precursors or calcination temperatures, are discussed.     

A novel method for the synthesis of chiral epoxides from styrene derivatives using chiral acids in presence of Pseudomonas lipase G6 [PSL G6] and hydrogen peroxide

Chiral epoxidation of styrene and its derivatives was carried out using series of chiral acids and urea hydrogen peroxide (UHP) or aqueous hydrogen peroxide (50%) in two phases under the catalytic influence of immobilized Pseudomonas lipase G6 [PSL G6] at 25-55 °C. A moderate to good yield and enantioselectivities of chiral epoxides were obtained.     

Amperometric biosensor for hydrogen peroxide based on hemoglobin entrapped in titania sol-gel film

Hemoglobin (Hb) was entrapped in a titania sol-gel matrix and used as a mimetic peroxidase to construct a novel amperometric biosensor for hydrogen peroxide. The Hb entrapped titania sol-gel film was obtained with a vapor deposition method, which simplified the traditional sol-gel process for protein immobilization. The morphologies of both titania sol-gel and the Hb films were characterized using scanning electron microscopy (SEM) and proved to be chemically clean, porous, homogeneous. This matrix provided a biocompatible microenvironment for retaining the native structure and activity of the entrapped Hb and a very low mass transport barrier to the substrates. H₂O₂ could be reduced by the catalysis of the entrapped hemoglobin at −300 mV without any mediator. The reagentless H₂O₂ sensor exhibited a fast response (less than 5 s) and sensitivity as high as 1.29 mA mM⁻¹ cm⁻². The linear range for H₂O₂ determination was from 5.0×10⁻⁷ to 5.4×10⁻⁵ M with a detection limit of 1.2×10⁻⁷ M. The apparent Michaelis-Menten constant of the encapsulated hemoglobin was calculated to be 0.18±0.02 mM. The stability of the biosensor was also evaluated.     

Large-scale preparation of ordered titania nanorods with enhanced photocatalytic activity

A titania layer with ordered nanostructures is expected to be of high photocatalytic activity due mainly to its high specific surface area. In the present work, large-area films with ordered titania nanorods were deposited on titanium substrates through a solution approach. The nanorods, with the phase composition of a mixture of anatase and rutile, grew on top of a condensed anatase interlayer along mainly the rutile [001]-axis. The photocatalytic activity was evaluated by decomposing rhodamine B in water and compared with the general sol-gel derived titania films and a commercial DP-25 titania coating. It is found that the as-deposited titania nanorods exhibited extremely high initial photocatalytic activity but declined to a poor value after the consumption of beneficial oxidative peroxo complexes coordinated to Ti(IV). A subsequent thermal treatment eliminated such complexes but at the same time improved the crystallinity of the titania nanorods. The photocatalytic activity of the thermally treated titania nanorods was stable and significantly higher than that of the sol-gel derived film and commercial DP-25 coating.     

Thermal evolution of (Zr,Ti)O2 gels synthesized at different basicpH

(Zr, Ti)O₂ gels as precursors of zirconium titanate (ZT) powders were prepared by the sol-gel method, which involves hydrolysis of ZrClO₂+TiCl₄ in the presence or absence of hydrogen peroxide, in twopH ranges, 8–9 or 11–12. Thermal evolution of these precursors has been studied by DTA, BET surface area, XRD and SEM. Differences in DTA curves, surface area and morphology were observed. In particular, ZT prepared atpH=8–9 with hydrogen peroxide was purer, more homogeneous and presented a different morphology compared to ZT processed atpH=11–12; hydrated/hydroxylated Zr?Ti species were formed to a greater extent in the latter case. Addition of hydrogen peroxide during chemical processing of these gels plays a key role in controlling the crystallization temperature of ZT.     

Synthesis of high surface area potassium hexatitanate powders by sol-gel method

Potassium hexatitanate (K₂Ti₆O₁₃) powders were synthesized by sol-gel method using supercritical drying to produce ion-exchangeable fine powders with high surface area. The effects of titanium alkoxides and mole ratios of K/Ti were investigated. By using sol-gel method, potassium hexatitanate powders were obtained at 630°C which is 350°C lower than that by melting method. The surface area of this sample was about 30–40 m²/g which was higher than that of melting method sample. Addition of H₂O and decrease in mole ratios of K/Ti increased surface area of powders.This work was partially supported by the IAEA (Research Program on Waste Treatment Immobilization Technologies Involving Inorganic Sorbent) contract. Many thanks to the IAEA's support.     

Preparation and Characterization of Porous Titania by Modified Sol-Gel Method

Mesoporous titania, especially anatase, is attractive due to its potential applications. A novel method to control pore structure of titania, surfactant- or polymer modification, is proposed. The wet gels and gel films, prepared from Ti(O-nC₄H₉)₄ were dried at 90°C and annealed at 500°C after immersion in surfactant or polymer solutions, and mesoporous anatase was obtained. The pore size, pore volume and specific surface area of the surfactant-modified bulk gels, estimated from N₂ absorption-desorption curves, are more than twice larger than those of the gels without modification. The pore size of the surfactant-modified gel films, observed by SEM, are similar to that of the bulk gels. The pore size obviously depended on the size of micelles. The pore size of the gels modified with hydrophilic polymers hardly increased, but the pore volume and the specific surface area increased.     

Sol-gel processed barium titanate waveguides

Monolayer monomode and multilayer multimode BaTiO₃ waveguides have been prepared on amorphous silica substrates by using the dip-coating technique and the sol-gel process. After heat treatment, these waveguides were hard and of good optical quality (losses as low as 2.6 dB/cm were measured) but, their structure was found to depend strongly on the number of layers. Monolayer waveguides were totally amorphous even when heated at 1000°C, while multilayer ones exhibited the tetragonal BaTiO₃ structure at an annealing temperature of 600°C.     

Nanocomposites NiFe2O4/SiO2 and CoFe2O4/SiO2-Preparation by Sol-Gel Method and Physical Properties

This paper aims to characterise the systems NiFe₂O₄/SiO₂ and CoFe₂O₄/SiO₂ prepared by the sol-gel method. After heat treatment, the various samples have been studied by means of X-ray diffraction, Mössbauer spectroscopy, magnetic measurements and transmission electron microscopy (HR TEM).X-ray diffraction and Mössbauer spectra confirmed the presence of the spinel phase. HR TEM observations revealed the nanocrystals with the size in the range of 2–25 nm. Magnetic measurements showed a superparamagnetic behaviour of the samples heated at lower temperature (800°C) and ferrimagnetic character for the samples heated at higher temperature (900, 1000°C).The final phase composition of the heated samples depends on the preparation conditions. The samples, treated up to 300°C in vacuum and then subsequently heated at 800°C or 900°C, do not contain hematite (the most stable phase at higher temperatures). On the contrary, the samples heated at 1000°C or 1250°C display certain content of hematite.     

Chemistry-Crystallization-Microstructure Relations of Sol-Gel Derived Lanthanum Modified Lead Titanate Thin Films

Lanthanum modified lead titanate thin films have been obtained by the deposition of sol-gel solutions onto platinized (100) silicon substrates. Crystallization of perovskite films was achieved by thermal treatments at 650°C with slow or rapid heatings. Lead oxide excesses were used in the precursor solutions to counterbalance the lead losses produced during the thermal treatment. Rapid heatings and large excesses of lead produce a preferred orientation of the films. These films have more homogeneous and denser microstructures than slow heated films without lead excess.     

Synthesis and characterization of nitric oxide-releasing sol-gel microarrays

Diazeniumdiolate-modified sol-gel microarrays capable of releasing low levels of nitric oxide are reported as a viable means for improving the blood compatibility of a surface without fully modifying the underlying substrate. Several parameters are characterized including: (1) NO surface flux as a function of sol-gel composition and microarray geometry; (2) microstructure dimensions and spacing for optimal blood compatibility; and (3) the effect of sol-gel surface modification on analyte accessibility to platinum electrodes. The sol-gel microarrays release biologically relevant levels of NO under physiological conditions for >24 h. In vitro platelet adhesion assays indicate that a NO surface flux of 2.2 pmol cm(-2) s(-1) effectively reduces platelet adhesion to glass substrates modified with sol-gel microstructures separated by 50 microm. The blood compatibility observed for these micropatterned surfaces is comparable to NO-releasing sol-gel films. When the separation between NO-releasing microstructures is reduced to 10 microm, the NO surface flux required to reduce platelet adhesion is lowered to 0.4 pmol cm(-2) s(-1). Finally, the oxygen response of platinum electrodes modified with NO-releasing sol-gel microarrays indicates that selective modification via micropatterning enhances analyte accessibility to the sensor surface.     

Titania on Silica. A Comparison of Sol-Gel Routes and Traditional Methods

Titania on silica samples have been prepared by: i) precipitation-deposition from a solution of TiCl₃ onto the surface of a commercial silica, and ii) base catalysed hydrolysis-condensation of TEOS followed by reaction with Ti isopropoxide. These samples were characterised by nitrogen and hydrogen adsorption, X-ray diffraction, FTIR, temperature programmed reduction, transmission electron microscopy and catalytic activity in butane-hydrogen conversion. The sol-gel preparation produced a better titania dispersion due to the formation of stabilising Ti-O-Si bonds. Upon these samples was then introduced Ir. Strong metal-support interactions between Ir and titania have been observed after high temperature reduction, causing a significantincrease in butane dehydrogenation activity relative to hydrogenolysis.It appears that using sol-gel chemistry useful supports for catalytic metals containing Si-O-Ti linkages can be produced and in future may be optimised for other metal-oxygen metal pairs.     

Influences of Heating Condition and Substrate-Surface Roughness on the Characteristics of Sol-Gel-Derived Hydroxyapatite Coatings

A prepared transparent HA solution was coated on Ti6Al4V substrates by a spin-coating technique. The crystallization of the sol-gel-derived HA coated on the metallic substrates could be done at relatively low firing temperatures (as low as 600°C). The characteristics of the HA-coated layer were dependent on the surface roughness of substrates and heating conditions such as firing temperature, holding time, heating rate, and atmosphere. The heat treatment at a slow heating rate (<2°C/min.) and a long heating time (>10 hrs) at 600°C in air produced the uniform surface and improved the crystallinity. The HA layer coated on 20 m grit-blasted substates was more uniform and had fever cracks after firing, compared with that coated on 100 m grit-blasted rougher substrates.     

Crystalline lanthanum hydroxycarbonates with controlled phases and varied morphologies prepared on non-crystalline substrates

Lanthanum hydroxycarbonate crystals with controlled phases and varied morphologies were prepared on the surface of a non-crystalline substrate, glass. The phases and morphologies of the crystals were controlled conveniently by varying the reaction temperature and the quantity of starting materials. Orthorhombic crystals were obtained at 160 °C, distributed individually on the substrate and had a flaky rhombic shape. Hexagonal crystals were obtained at 180 °C. The crystals had a rhomboidal shape, were uniform and continuous enough to form a solid film on the substrate. The substrates were corroded under the hydrothermal conditions and offered a coarse surface for the crystal growth. The hexagonal lanthanum hydroxycarbonate was discovered to show significant second harmonic generation, which would be of interest for developing novel optical materials.