Titania Silica Mixed Oxides Research Articles

Determination of surface acidity of mixed oxide of silicon and titanium by calorimetric titration

Silica-titania mixed oxide with catalytic and adsorption properties has been of great academic and industrial interest. Metal oxides supported on silica have been used as a matrix for immobilizing electron transfer mediators, generating materials with diverse properties. The characterization of the surface acidity of these materials is essential and has been carried out using various techniques, including IR spectroscopy and calorimetry. However, no single technique completely analyses the present acidic sites. This study used calorimetric titration to investigate a mixed oxide containing titanium and silica, prepared by the sol-gel method, and its interaction with pyridine. The results showed that thermal treatment increased the enthalpy values (ΔH), indicating water removal from the matrix surface. The presence of pyridine resulted in a decrease in ΔH values, suggesting a preferential occupation of the stronger acidic sites. After thermal treatments between 473 and 573 K, the solids exhibited similar ΔH values, indicating a homogenization of the surface acidic sites. Calorimetric analysis revealed that the acidic sites were occupied in descending order of strength, with the strongest sites being filled initially. The increase in temperature did not result in new acidic sites but rather in greater occupation of the existing ones. Correlation between calorimetric and infrared data is suggested as the next investigation step. Thus, the results of this study contribute to a deeper understanding of the physicochemical properties, especially regarding their surface acidity, with the potential for more effective and controlled practical applications of this silica-titania mixed oxide in catalysis and adsorption.

Characterization of spherical silica–titania mixed oxide particles synthesized by using a dry process

Silica–titania mixed oxides have excellent properties, such as a low thermal expansion coefficient and a refractive index that can be adjusted by changing the Ti content. However, when the Ti content increases, silica and titania phases in silica–titania mixed oxides can separate. This phase separation leads to the precipitation of the titania component as rutile or anatase crystals. When silica–titania mixed oxides undergo phase separation, their properties become unstable; for example, the refractive index of the particles becomes non-uniform. Therefore, it is preferable to synthesize silica–titania mixed oxides in an amorphous state without causing phase separation. Based on our previous studies on particle size control in silica synthesis, we employed a dry process using organosilicon compounds to synthesize silica–titania mixed oxides. In this study, spherical amorphous silica–titania mixed oxide particles were obtained via flame synthesis using organosilicon and organotitanium compounds. The purpose of this study was to characterize the obtained powder and explore the possibility of controlling particle size during synthesis. By studying the dry process synthesis of spherical silica–titania mixed oxide particles, we confirmed the relationships: between the Si/Ti molar ratio and the obtained crystal structure and between the adiabatic flame temperature and the particle size.

A Kinetic Study of Photocatalytic Degradation of Phenol over Titania–Silica Mixed Oxide Materials under UV Illumination

A set of titania–silica mixed oxide materials were prepared by a cosolvent-induced gelation method using ethanol and toluene as solvent and cosolvent, respectively. These materials were extensively characterized by utilizing several characterization techniques and assessed for phenol degradation under UV illumination. The degradation of phenol follows first-order kinetics, and fragmented products formed during the phenol degradation were qualitatively identified by using high performance liquid Chromatographic (HPLC) and atomic pressure chemical ionization mass spectroscopic (APCI-MS) techniques. The complete mineralization of phenol was further evidenced by the measurement of the total organic contents that remained in the solution after irradiation. The pore diameter of the materials was found to be the key factor for phenol degradation, whereas surface area and pore volume play a role among the mixed oxide materials. In addition, in the mixed oxide system there was an inverse correlation obtained with the particle size of the materials and the degradation efficiency. The smaller particle size of titania in the mixed oxide material was found to be a requirement for an effective degradation of phenol.

Electrokinetic properties of silica-titania mixed oxide particles dispersed in aqueous solution of C.I. Direct Yellow 142 dye – effects of surfactant and electrolyte presence

Electrokinetic properties of silica-titania mixed oxide particles dispersed in aqueous solution of C.I. Direct Yellow 142 dye – effects of surfactant and electrolyte presence

Laser ablation of silicon monoxide and titanium monoxide in liquid: formation of mixed colloidal dispersion with photocatalytic activity

Silica–titania mixed oxides and composites have been extensively studied, whereas to the titanium monoxide (TiO) –silicon monoxide (SiO) counterparts has been devoted very little attention. Laser ablation of SiO and TiO in liquids is in according with literature completely unexplored. Here we report on Nd:YAG pulse laser ablation of SiO and TiO in ethanol which allows generation of SiO- and TiO-based nanoparticles and their agglomerates.Mixed SiO-TiO colloid has been prepared by simple mixing of ablatively prepared individual colloids in 1:1 volume ratio. Measurement of size distribution by Dynamic Light Scattering (DLS) determines sizes of 24.85 nm and 262.3 nm for SiO colloid, 494.8 nm for TiO colloid and 35.2 nm and 397.5 nm for mixed colloid. Zeta potential values suggest incipient instability for all measured systems. Morphology of the particles captured on Ta substrate by evaporation of ethanol was studied using Scanning Electron Microscopy (SEM). Round-shaped, oval, and sheet-like particles and their agglomerates have been observed. Raman spectroscopy of the mixed SiO-TiO colloid revealed multiphase structure consisting of anatase and/or rutile, crystalline and amorphous silicon and silica and crystalline and amorphous titanium silicide TiSi2. Formation of TiSi2 demonstrates unexpected low temperature disproportionation of SiO and TiO-based species and mutual reducing interactions. Catalytic activity of individual SiO and TiO colloids and of their mixture has been tested in terms of methylene blue (MB) degradation under the daylight. TiO-SiO mixture exhibits higher solar-light catalytic activity compared to individual colloids which could by explain by the presence of highly photocatalytic TiSi2. These results represent potential of SiO and TiO reducing interactions which are favorable for generation of photocatalytic materials for water remediation.

Energy and electron transfer reactions on silica gel and titania\u2013silica mixed oxide surfaces

The energy and electron transfer reactions of anthracene co-adsorbed with an electron donor on silica gel and titania–silica mixed oxides have been studied by a combination of steady-state reflectance, emission spectroscopy, and nanosecond diffuse reflectance laser flash photolysis. Bimolecular rate constants for energy and electron transfer between anthracene and azulene have been measured; kinetic analysis of the decay of the anthracene triplet state and radical cation show that the kinetic parameters depend on the titania content of the sample and the azulene loading. The rate of energy and electron transfer reactions increases as a function of azulene loading and decreases with increasing titania content in titania–silica mixed oxides. These findings indicate that the observed rate of reaction is determined by the rate of diffusion of anthracene on the titania–silica surfaces, whereas, in contrast, the observed rate of reaction on silica gel is predominantly governed by the rate of diffusion of azulene.Graphic abstract

Thermal reactions in mixtures of micron-sized silicon monoxide and titanium monoxide: redox paths overcoming passivation shells

Silica–titania mixed oxides and composites have been extensively studied, whereas the titanium monoxide (TiO)–silicon monoxide (SiO) counterparts still remain to be explored. Here, we report on structural changes in heated SiO–TiO mixtures. The changes in composition in intimately mixed μm-sized particles of TiO and SiO heated at 1000 °C were examined by FTIR, UV–Vis and Raman spectroscopy, X-ray diffraction and electron (SEM and TEM) microscopy. They are shown to involve depletion of crystalline TiO and formation of titanium suboxides (Ti2.5O3, Ti2O3), rutile, elemental silicon, titanium silicide Ti5Si3 and amorphous binary SiO x , TiO x and ternary Si x Ti y O z nano-structures. These constituents of the developed Si/Ti/O composite are explained by SiO disproportionation, reduction of TiO by silicon, oxygen transfer (redox) reactions between TiO x and SiO x species and the combination of Ti and Si to obtain titanium silicide. The produced Si/Ti/O composite absorbs visible light and its solar-light photocatalytic activity in decolorization of methylene bBlue is compared to that of the unheated SiO, TiO and Ti5Si3 powders.

CW-Laser-Induced Solid-State Reactions in Mixed Micron-Sized Particles of Silicon Monoxide and Titanium Monoxide: Nano-Structured Composite with Visible Light Absorption

Silica–titania mixed oxides and composites have been broadly examined for their physical and catalytic properties, but titanium monoxide–silicon monoxide counterparts have yet drawn very little attention. Here we report that laser-induced processing of mixed silicon and titanium monoxides results in reactions yielding a nanostructured Ti/Si/O composite absorbing visible light. Changes in the composition of intimately mixed μm-sized particles of silicon monoxide (SiO) and titanium monoxide (TiO) induced by scanning of a cw CO2 laser beam along the TiO–SiO pellet surface were examined by FTIR and Raman spectroscopy, X-ray diffraction and electron microscopy. They are shown to consist in the evolution of TiO2 (rutile and anatase), titanium suboxides (Ti4.5O5, Ti2O3), silica and amorphous binary SiOx, TiOx and ternary SixTiyOz nano-phases which contain less or more O than SiO and TiO monoxides. These products are ascribed to concurrent silicothermal reduction of TiO and O-transfer between SiO and TiO due to interdiffusion of Si- and Ti-based species. These reactions taking place under transient localized heating are not inhibited by passivation shells around SiO and TiO particles. The laser-produced Ti/Si/O composite shows absorption band at 425 nm tailing up to 1100 nm. Its solar-light photocatalytic activity in decolorization of Methylene Blue is compared to that of the unheated SiO and TiO powders absorbing only in UV region.

Titania–silica mixed oxides investigated with density functional theory and molecular dynamics simulations

AbstractMixed phases of titania and silica have raised interest for their high activity as photocatalysts and for their optical properties, such as a high refractive index. To rationalize their properties, it is necessary to understand their atomic structure in crystalline and amorphous phases. We have investigated Ti–Si mixed oxide phases by density functional theory and molecular dynamics. A polarizable potential has been developed for and has been employed to sample the configuration space. Mixed phases are metastable with respect to separate and , but they are only slightly higher in energy, and therefore might form under technologically relevant conditions. All Ti–Si mixed oxides considered, regardless of cation coordination, display peaks in IR and Raman spectra in the region of frequencies 880–950, while Ti‐only phases do not, even if titanium is in a tetrahedral coordination. Our calculations thus confirm that these peaks are a signature of Ti–O–Si links, but they do not deliver information on the actual atomic structure of the material. Phases with titanium in a tetrahedral coordination display a higher electronic band gap than phases with titanium in octahedral coordination. This should have important consequences for the photocatalytic activity of mixed oxides of titania and silica.

Synthesis and characterization of new silica–titania mixed oxide in the presence of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide by sol–gel technique

Silica–titania mixed oxide were prepared by sol–gel method from tetraethylorthosilicate and titanium (IV) isopropoxide as precursors in the presence of room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C4MIm][NTf2]. The effects of [C4MIm][NTf2] on the structural and textural characteristics of silica–titania matrix are investigated in this paper. The materials obtained were well characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis X-ray powder diffraction (XRPD), field emission scanning electron microscope (FESEM) and N2 adsorption–desorption analysis. It is believed that the [C4MIm][NTf2] plays an important role as a template and the high surface area of the samples is thought to mainly attribute to the formation of microporous in the reaction. The synthesized materials showed the presence of C–N groups in the FTIR spectrum which indicates the presence of RTIL in the silica–titania matrix. XRPD, FESEM and N2 adsorption–desorption analysis results indicated that the composite materials possessed good microporous character. The subsequent material displayed average pore diameter of 1.70–2.12 nm, pore volume of 0.08–0.19 cm3/g and BET surface area of 191–386 m2/g. Increasing the content of RTIL resulted in an increase of the average pore diameter of the silica–titania gel.

Effect of the type of acid used in the synthesis of titania–silica mixed oxides on their photocatalytic properties

TiO2–SiO2 mixed oxides were synthesized by the sol–gel technique using three different acids, i.e., acetic, sulfuric, or chlorhydric acid. Their photocatalytic behavior was evaluated on the phenol oxidation in liquid phase and correlated with the characterization results. It was found that the kind of acid used during the preparation strongly influences the phase composition and stability of the TiO2 phases incorporated in the silica structure as well as the photocatalytic activity. In all cases, silica introduced a dispersive effect that stabilized the TiO2 crystalline phases upon calcination at 700°C. SO42− and CH3COO− ions stabilized the anatase phase at high calcination temperatures (700°C) leading to samples with the highest photoactivities. Cl− ions induced the formation of traces of rutile and brookite resulting in a lower photoactivity. The highest photoactivity was achieved with the catalyst synthesized with acetic acid and calcined at 700°C (TS1-700-ace). The photocatalytic performance of this material was even better than that obtained with the commercial catalyst Degussa P-25.

Competitive role of structural properties of titania–silica mixed oxides and a mechanistic study of the photocatalytic degradation of phenol

TiO2–SiO2 mixed oxide materials were hydrothermally synthesized and the photocatalytic degradation of phenol under UV-irradiation was evaluated. We also demonstrated that varying the co-solvent, modulates the structural properties of the materials. In particular, the use of non-polar co-solvents such as toluene seemed to increase the crystallinity, surface area, and pore diameter while the crystallite size of titania seemed to change little. A comprehensive characterization using surface and bulk techniques evidenced the role of porosities, crystallinity, and Ti–O–Si linkages of the mixed oxides as significant factors that contribute to the degradation of phenol. The TiO2–SiO2 mixed oxide material prepared using only ethanol as the solvent showed 24% degradation of phenol after 120min of irradiation whereas other mixed oxide materials degraded phenol more efficiently (57% to 100%) in the same duration of time. The higher photocatalytic activities of the mixed oxide materials prepared using non-polar solvents is attributed to a combination of factors that include higher Apparent Surface Coverages of Ti–O–Si heterolinkages, larger pore sizes, and most importantly higher crystallinities of the titania phase. Larger pore sizes enabled better transport of reactant molecules and products to and from the active sites (Ti–O–Si heterolinkages) and the higher crystallinities of the titania phase helped in minimizing the electron–hole recombination in these photocatalysts, and thus resulted in high degradation efficiencies.

An investigation into the effect of porosities on the adsorption of rhodamine B using titania–silica mixed oxide xerogels

Aperiodic mesoporous titania–silica (TiO2·SiO2) xerogels with varying silica contents were synthesized under ambient conditions. The physico-chemical properties of the xerogels were examined by a variety of techniques that include powder X-Ray Diffraction (XRD), nitrogen adsorption, Fourier Transform-Infra-Red spectroscopy (FT-IR), Scanning and Transmission Electron Microscopies (SEM and TEM), Thermo Gravimetric Analysis (TGA), zeta potential, and Diffuse Reflectance Spectroscopic (DRS) studies. The adsorption of a model dye molecule, rhodamine B (RhB) was studied over the titania–silica xerogels and compared with titania and silica. It was determined that the pore volume of the xerogels mainly influences the adsorption of RhB. The xerogels exhibited good adsorption capacity with more than 90% dye removal at low dye concentrations. Our results suggest that low cost approaches to the synthesis of xerogels with tailored properties such as large pore volume could provide cost-effective solutions to mitigate environmental problems related to removal of water based toxic pollutants such as dyes by simple adsorption processes.

TiO2(SiO2)x and ZrO2(SiO2)x Cryogels as Catalysts for the Citronellal Cyclization to Isopulegol

TiO2(SiO2)x and ZrO2(SiO2)x mixed oxides prepared by a simple sol–gel procedure plus freeze-drying achieve very high surface areas. Such cryogels are shown to catalyze the cyclization of citronellal to isopulegol. The dispersion of the active metal has been optimized, as it is shown that high specific surface areas are the key for the catalytic activity of the cogels. Nevertheless zirconia–silica cryogels depict much higher catalytic activity, with only 5 mol% Zr being required, than the corresponding titania-silica mixed oxides.

Synthesis of titania–silica xerogels by co-solvent induced gelation at ambient temperature

A series of binary titania–silica mixed oxides was prepared by sol–gel synthesis at room temperature. The hydrolysis of titanium isopropoxide (Ti( i OPr) 4) and tetraethylorthosilicate (TEOS) was facilitated by co-solvent induced gelation in acidic media. The resulting gels were dried, calcined, and then characterized by powder X-ray diffraction analysis, nitrogen sorption studies (at 77 K), diffuse reflectance spectroscopy, Raman microscopy, and transmission electron microscopy. The nitrogen sorption studies indicate that the porosities could be tuned when simple aromatic solvents such as toluene, p-xylene, or mesitylene were added as a co-solvent to the synthesis gel. The binary mixed metal oxide materials obtained in this study showed high activity towards the degradation of phenol, and possessed high surface areas, and large pore volumes with narrow pore size distribution without the need for additional hydrothermal synthesis or supercritical drying.

ChemInform Abstract: Genesis and Structural Properties of Alkoxide-Prepared Titania-Silica Xerogels.

Titania–silica mixed oxide gels with a 1 : 4 Ti : Si molar composition were prepared from the hydrolysis of tetraethoxy orthosilicate (TEOS) and tetraisopropoxy orthotitanate (TIOT), using different amounts of water, acid or base, and hydrolysis procedure. Surface area, pore structure, and crystallinity were compared in relation to sol-gel process conditions. Gels in which the TEOS was hydrolysed using a basic medium possessed larger mesopores and correspondingly lower surface area than gels prepared with acid-hydrolysed TEOS, but were more resistant to mesopore collapse upon drying, owing to the spherically shaped silica subunits in these gels. Gels hydrolysed by a two-stage procedure, involving partial hydrolysis of TEOS in acid, followed by mixing with pure TIOT and completion of hydrolysis, are most susceptible to pore collapse upon drying, producing a completely microporous xerogel. Pore collapse did not occur when the wet-gel material was aged in slightly basic medium for several days. All gels prepared by the two-stage hydrolysis procedure remain X-ray amorphous after treatment in air at 870 K, whereas gels produced by mixing completely hydrolysed component sols show crystallization of the titania. Thermal analysis runs show water loss primarily results from weakly bound water. In general, a residual amount of unreacted alkoxy groups is present in gels prepared without a large excess of hydrolysis water. Highest residual organic amounts of 2–8 wt. % were found with the two-stage hydrolysed gels. Rutile was only detected in gels prepared in excess water, but the extent of rutile formation, as well as crystallite growth, is considerably less than in similarly prepared pure titania gels.

Characterisation and photocatalytic properties of titania–silica mixed oxides doped with Ag and Pt

TiO 2–SiO 2 mixed oxides have been synthesised and modified by Ag and Pt deposition. Due to the effect of the silica on the mixed oxide, the prepared materials presented high surface areas and stabilised anatase as the only crystalline phase after calcination at 700 °C. Even using the same photodeposition experimental conditions, the yield for metal deposition depended highly on the metal considered, being much lower for Ag deposition. XPS studies permitted to estimate metal dispersion and oxidation state of the different samples, being both factors of high importance regarding photocatalytic improvement by metal deposition.

Sol-Gel Titania and Titania-Silica Mixed Oxides Photocatalysts

This paper presents a review of the work published by the authors on the synthesis, characterization and evaluation of the photocatalytic activity of TiO2/SiO2 materials. The use of titania-silica mixed oxides photocatalysts is proposed basically as a process improvement to overcome the difficulties of recovering titania from the slurries after the photocatalytic treatment of contaminated waters. To understand the mechanism governing the photocatalytic activity of these materials, several titania-silica photocatalysts have been prepared through a sol-gel method that allows controlling the main variables to obtain materials with different textural properties, degree of titania incorporation, dispersion of the photoactive phase and crystallinity of titanium dioxide. The samples have been characterized in depth, looking for correlations between the main physicochemical properties (TiO2 crystallite size, band gap energy and titania surface area) and the activity shown in the photocatalytic oxidation of cyanide, selected as model pollutant. The results suggest that the photocatalytic activity is strongly influenced by the quality of the titania crystal network, which in turn is improved by the use of a hydrothermal crystallization procedure. Additionally, the evaluation of the fraction of the total surface area corresponding to titania is mandatory for comparing the catalytic activity of different materials in processes in which titanium dioxide is the only phase catalytically active and silica behaves as an inert support.

ChemInform Abstract: Selectivity Enhancement in Heterogeneous Catalysis Induced by Reaction Modifiers

Abstract The application range of solid catalysts can be greatly extended by reaction or process modifiers , that is by simple addition of an inorganic or organic compound to the reaction mixture. The modifier, used in catalytic amounts, ideally interacts strongly with the active sites in a fashion which induces favorable changes in the outcome of the reaction. Evolution of the actual modified metal catalyst during reaction and the importance of in situ characterization in understanding these processes are illustrated using the examples of promotion by metal ions and nitrogen-containing bases. The major part of the review describes the advantages and limitations of employing N-base modifiers for tuning the performance of solid catalysts. Reactions discussed include chemo-, stereo-, enantio- and diastereoselective hydrogenations over metal catalysts, aerobic oxidation of alcohols with Pt and Pd, and epoxidation of allylic alcohols with titania–silica mixed oxides and alkyl hydroperoxides.

Cultivation of human fibroblasts and multipotent mesenchymal stromal cells on mesoporous silica and mixed metal oxide films

The application of mesoporous silica and silica–titania-mixed metal oxide films prepared via sol–gel processing as substrates for cell growth was investigated. A deliberate tailoring of the chemical composition of the porous substrates with different Si:Ti ratios was achieved by using a single-source precursor based on a titanium-coordinated alkoxysilane, resulting in mesoporous silica–titania films with hydrophilic surfaces. The different coatings were investigated with respect to their applicability in the cultivation of human cells such as human fibroblasts and multipotent mesenchymal stromal cells. It was found that they promoted cell adhesion and proliferation of human fibroblasts up to a period of 14 days. After 2 weeks only single apoptotic cells could be detected on silica–titania mixed oxide films in contrast to a somewhat higher amount on silica coatings. Furthermore, none of the films inhibited osteogenic differentiation of multipotent mesenchymal stromal cells.