Properties of TiO2 prepared by acid treatment of BaTiO3

TiO₃ powders were prepared by acid treatment of BaTiO₃ and their properties were investigated. The BaTiO₃ powder was subjected to HNO₃ in concentrations ranging from 10⁻³ to 8 M at 90 °C for 0.5-6 h. Dissolution of BaTiO₃ and precipitation of TiO₂ occurred at acid concentrations of 2-5 M. BaTiO₃ dissolves completely to form a clear solution at reaction times of 0.5-1 h, but a rutile precipitate is formed after 2 h of acid treatment. By contrast, anatase is precipitated by adjusting the pH of the clear solution to 2-3 using NaOH or NH₄OH solution. The rutile crystals were small and rod-shaped, consisting of many small coherent domains connected by grain boundaries with small inclination angles and edge dislocations, giving them a high specific surface area (S_BET). With increasing HNO₃ concentration, the S_BET value increased from 100 to 170 m²/g while the crystallite size decreased from 25 to 11 nm. The anatase crystals obtained here were very small equi-axial particles with a smaller crystallite size than the rutile and S_BET values of about 270 m²/g (higher than the rutile samples). The photocatalytic activity of these TiO₂ was determined from the decomposition rate of Methylene Blue under ultraviolet irradiation. Higher decomposition rates were obtained with larger crystallite sizes resulting from heat treatment. The maximum decomposition rates were obtained in samples heated at 500-600 °C. The photocatalytic activity of the TiO₂ was found to depend more strongly on the sample crystallite size than on S_BET.     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

Facile synthesis of mesoporous core-shell TiO2 nanostructures from TiCl3

The present study reports the synthesis and formation process of mesoporous core-shell TiO₂ nanostructures by employing a glucose-assisted solvothermal process using water-ethanol mixture as solvent and subsequent calcination process at 550 °C for 4 h. X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption analysis were used to investigate the structural properties of these nanostructures. By optimizing the preparation conditions, especially the contents of water and ethanol in the mixture solvent, mesoporous core-shell TiO₂ nanostructures were obtained. These mesoporous nanostructures have anatase phase and exhibit the superior photocatalytic activity. This synthesis route is facile due to the usage of stable and low-cost Ti precursor such as TiCl₃ and is thus applicable for large-scale production.     

Morphologies and crystal structures of nano-sized Ba1−xSrxTiO3 primary particles prepared by flame spray pyrolysis

Nano-sized Ba_1−xSr_xTiO₃ (BST) powder was prepared by flame spray pyrolysis using “CA-assisted” spray solution. The effects of the mole ratios of Ba to Sr components on the mean sizes, morphologies, and crystal structures of the BST powder prepared by flame spray pyrolysis were investigated. The precursor powders obtained by flame spray pyrolysis had large size, fractured and hollow structures irrespective of the mole ratios of Ba to Sr components. The post-treated BST powders had slightly aggregated morphology of the primary particles with nanometer sizes. The slightly aggregated BST powders turned to nano-sized primary particles by a simple milling process. The milled BaTiO₃ particles post-treated at temperature of 1000 °C had spherical-like shape. On the other hand, the milled Ba_0.5Sr_0.5TiO₃ and SrTiO₃ particles had square shape. The mean sizes of the milled BaTiO₃, Ba_0.5Sr_0.5TiO₃ and SrTiO₃ particles were each 110, 32, and 48 nm. Phase pure BST powder was obtained at a post-treatment temperature of 1000 °C irrespective of the mole ratios of Ba to Sr components. The BaTiO₃ powder had tetragonal crystal structure. On the other hand, the BST except for the BaTiO₃ composition had cubic crystal structures at post-treatment temperature of 1000 °C. The mean crystallite sizes of the milled Ba_1−xSr_xTiO₃ primary particles were changed from 29 to 37 nm according to the mole ratios of Ba to Sr components.     

Preparation, characterization and photocatalytic activity of in situ Fe-doped TiO2 thin films

Fe-doped TiO₂ thin films were prepared in situ on stainless steel substrates by liquid phase deposition, followed by calcination at various temperatures. It was found that some Fe³⁺ ions were in situ doped into the TiO₂ thin films. At 400 °C, the film became photoactive due to the formation of anatase phase. At 500 °C, the film showed the highest photocatalytic activity due to an optimal Fe³⁺ ion concentration in the film. At 900 °C, the photocatalytic activity of the films decreased significantly due to the further increase of Fe³⁺ ion concentration, the formation of rutile phase and the sintering and growth of TiO₂ crystallites.     

Photocatalytic degradation of dyes and organic contaminants in water using nanocrystalline anatase and rutile TiO2

Nanocrystalline TiO₂ was synthesized by controlled hydrolysis of titanium tetraisopropoxide. The anatase phase was converted to rutile phase by thermal treatment at 1023 K for 11 h. The catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared absorption spectrophotometry (FT-IR) and N₂ adsorption (BET) at 77 K. This study compare the photocatalytic activity of the anatase and rutile phases of nanocrystalline TiO₂ for the degradation of acetophenone, nitrobenzene, methylene blue and malachite green present in aqueous solutions. The initial rate of degradation was calculated to compare the photocatalytic activity of anatase and rutile nanocrystalline TiO₂ for the degradation of different substances under ultraviolet light irradiation. The higher photocatalytic activity was obtained in anatase phase TiO₂ for the degradation of all substances as compared with rutile phase. It is concluded that the higher photocatalytic activity in anatase TiO₂ is due to parameters like band-gap, number of hydroxyl groups, surface area and porosity of the catalyst.     

Temperature dependence of magnetic property and photocatalytic activity of Fe3O4/hydroxyapatite nanoparticles

Fe₃O₄/hydroxyapatite (HAP) nanoparticles have been developed as a novel photocatalyst support, based on the embedment of magnetic Fe₃O₄ particles into HAP shell via homogeneous precipitation method. The resultant nanoparticles were characterized by transmission electron microscope (TEM) and X-ray diffraction (XRD). These particles were almost spherical in shape, rather monodisperse and have a unique size of about 25 nm in diameter. The effect of calcination temperature on magnetic property and photocatalytic activity of Fe₃O₄/HAP nanoparticles was investigated in detail. The obtained results showed that the Fe₃O₄/HAP nanoparticles calcined at 400 °C possessed good magnetism and photocatalytic activity in comparison with that calcined at other temperatures.     

Phase transformation in semi-transparent TiO2 films irradiated with CO2 laser

Anatase (TiO₂) thin films were obtained by immersion of glass plates into a titanium sol-gel precursor followed by calcination at 450 °C for 3 h. The Raman results for the CO₂ laser irradiated TiO₂ films show that laser radiation is able to promote favorable changes of anatase phase in anatase/rutile mixtures. Nevertheless, the transformation process level depends on laser characteristics and scan speed of the radiation treatment.     

A low-temperature process to synthesize rutile phase TiO2 and mixed phase TiO2 composites

This works employed K₂Ti₄O₉, a novel Ti source, to prepare TiO₂ powders. By a “low-temperature dissolution-reprecipitation process” (LTDRP), rutile phase TiO₂ was successfully synthesized after reacting at 50 °C for 48 h. The obtained sample showed a specific surface area about 45 m²/g, and excellent activity in photo-destruction of NO_x gas. The coupling of rutile phase TiO₂ with commercial anatase TiO₂ showed significant effect in further enhancing the photocatalytic activity.     

Controllable synthesis and photocatalytic activities of water-soluble TiO2 nanoparticles

Water-soluble anatase, mixed-phase (anatase and rutile) and rutile TiO₂ nanoparticles (NPs) or nanorods were synthesized under mild solution conditions using polyethylene glycol 400 (PEG 400) as a stabilizer and HCl as a phase controlling reagent. The photocatalytic properties of these NPs with different crystal phases were evaluated by photocatalytic degradation experiments of methyl orange (MO). As-prepared pure anatase TiO₂ NPs show a higher photocatalytic activity than other samples and commercial P25, which may be related to the high crystallinity, the pure anatase phase, small size and the enhanced absorbability associated with the existence of PEG 400 on the NP surface.     

In situ derivation of sulfur activated TiO2 nano porous layers through pulse-micro arc oxidation technology

Micro arc oxidation technique, as a facile and efficient process, was employed to grow sulfur doped titania porous layers. This research sheds light on the photocatalytic performance of the micro arc oxidized S-TiO₂ nano-porous layers fabricated under pulse current. Morphological and topographical studies, performed by SEM and AFM techniques, revealed that increasing the frequency and/or decreasing the duty cycle resulted in formation of finer pores and smoother surfaces. XRD and XPS results showed that the layers consisted of anatase and rutile phases whose fraction was observed to change depending on the synthesis conditions. The highest anatase relative content was obtained at the frequency of 500 Hz and the duty cycle of 5%. Furthermore, photocatalytic activity of the layers was examined by measuring the decomposition rate of methylene blue under both ultraviolet and visible photo irradiations. Maximum photodegradation reaction rate constants over the pulse-grown S-TiO₂ layers were respectively measured as 0.0202 and 0.0110 min⁻¹ for ultraviolet and visible irradiations.     

Heat treatment of nanometer anatase powder and its photocatalytic activity for degradation of acid red B dye under visible light irradiation

The phase transformation of nanometer TiO₂ powder from anatase to rutile was realized by heat treatment, and a new nanometer TiO₂ photocatalyst that could be excited by visible light was obtained. The heat-treated TiO₂ powder at different transition stage was characterized by powder x-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. The test of photocatalytic activity of the heat-treated TiO₂ powder was carried out by the photocatalytic degradation of acid red B dye in aqueous solution under visible light irradiation. The nanometer anatase TiO₂ heat-treated at 500°C for 30 min exhibited much higher activity than those of pure anatase and mechanically mixed (anatase and rutile) TiO₂. The remarkable improvement of photocatalytic activity was mainly illustrated by the special interphase between rutile and anatase, which not only restrains the recombination of photogenerated electron-hole pairs but also reduces the adsorbability of nanometer anatase TiO₂ powder to a certain extent. More significantly, the anticipatory interlaced energy level of heat-treated TiO₂ particles is convenient for capturing photons of low energy and thus achieves the intention of using visible light. The text was submitted by the authors in English.     

Preparation and photocatalytic activity of TiO2 powders from titanium citrate complex using two-step hydrothermal treatments

White, almost carbon-free TiO₂ powders were prepared from a titanium citrate complex ((NH₄)₄[Ti₂(C₆H₄O₇)₂(O₂)₂]·4H₂O) using a two-step hydrothermal treatment. The product yield, carbon contamination, and crystalline phase of TiO₂ depended on both the temperature and pH value for each treatment. Titanium was precipitated as a solid phase (H₂Ti₂O₅·H₂O) using the first hydrothermal treatment in the basic condition (pH = 12) at temperatures less than 150 °C. Then white rutile or anatase powder was crystallized using the second hydrothermal treatment at 200 °C. By changing the pH condition of the second hydrothermal treatment, rutile and anatase were synthesized selectively. The photocatalytic decomposition activity of obtained rutile powder for gaseous 2-propanol under visible light was increased by Cu-grafting.     

Third-order optical nonlinearities in anatase and rutile TiO2 thin films

Titanium dioxide (TiO₂) films have been fabricated on fused quartz and Si(001) substrates by pulsed laser deposition technique and the single-phase anatase and rutile films were obtained under the optimal conditions. The surface images and optical transmission spectra were investigated by scanning electron microscopy and double beam spectrophotometer, respectively. The values of optical band-gap and linear refractive index of the anatase and rutile films were determined. The optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. Through the open-aperture and closed-aperture Z-scan measurements, the real and imaginary parts of the third-order nonlinear optical susceptibility were calculated and the results show that the anatase phase TiO₂ films exhibit larger nonlinear refractive effects compared with rutile phase. The figure of merit, T, defined by T = βλ/n₂, was calculated to be 0.8 for anatase films, meeting the requirement of T < 1 and showing potential applications in all-optical switching devices.     

TiO2 nanorod films grown on Si wafers by a nanodot-assisted hydrothermal growth

We report the controlled hydrothermal growth of rutile TiO₂ nanorods on Si wafers by using an anatase TiO₂ nanodot film as an assisted growth layer. The anatase nanodot film was prepared on the wafer by phase-separation-induced self-assembly and subsequent heat-treatment at 500 °C. The nanodots on the wafer were then subjected to hydrothermal treatment to induce the growth of rutile TiO₂ nanorod films. The size and dispersion density of the resulting TiO₂ nanorods could be varied by adjusting the Ti ion concentration in the growth solution. The TiO₂ nanorods were of the rutile phase and grew in the [001] direction. The growth mechanism reveals that the growth of the rutile nanorods was wholly dependent on the existence of rutile TiO₂ seeds, which could be formed by the dissolution-reprecipitation of the anatase nanodots during hydrothermal treatment or under the high-temperature conditions of the subsequent heat-treatment of the as-prepared nanodots. In controlling the rutile nanorod growth, the anatase nanodots show more efficiency than a dense anatase film. Preliminary evaluations of the rutile nanorod films have demonstrated that the wettability changed from highly hydrophobic to superhydrophilic and that the photocatalytic activity was enhanced with increasing nanorod dispersion density.     

Synthesis and photocatalytic activity of nanocrystalline TiO2-SrO composite powders under visible light irradiation

Nano-sized homogeneously distributed TiO₂-20, -40, -60 wt.% SrO composite powders were successfully synthesized by a sol-gel method. The as-received amorphous TiO₂—20 wt.% SrO composite powders were crystallized with anatase TiO₂ at around 750 °C. As calcination temperatures increased, the anatase TiO₂ crystalline phase was transformed to rutile TiO₂ at about 900 °C, whereas nano-sized, squarish SrTiO₃ phase was detected. The peaks obtained after calcining at 1050 °C mainly exhibited the rutile TiO₂ and SrTiO₃ phases. However, a small number of SrO₂ peaks were also detected. For the comparison of photocatalytic activity depending on light sources, TiO₂-SrO composite powders were tested in phenol degradation. TiO₂-60 wt.% SrO composite powder showed good visible light photoactivity for the photo-oxidation of phenol.     

Effect of TiCl4 concentration on the structure of its aqueous solutions and on the properties and photoactivity of derived nanocrystalline titania

The influence of the concentration of aqueous TiCl₄ solution on the phase formation, morphology and particle size of the titanium dioxide hydrolysis product was investigated by XRD and TEM. Significant features, observed in the Raman spectra of the TiCl₄ solutions with a concentration >3 M, demonstrated that the TiCl₄ had hydrolysed. As the formal concentration of TiCl₄ decreased from 4.98 to 1 M, the Raman spectra changed qualitatively. Despite the changes in the Raman spectra of these precursor solutions, the TiO₂ product was mainly rutile in all cases. However, at low TiCl₄ concentrations small amounts of anatase were also observed. Electron microscopy suggested that the anatase particles were significantly smaller than the rutile and also indicated increasing aggregation of the product from the more dilute TiCl₄ solutions. The optical properties and photoactivities of the TiO₂ powders prepared at different concentrations were also investigated. The powder synthesized from 5 M TiCl₄ showed the highest UV extinction. The photoactivity of the product, determined by the photocatalytic oxidation of propan-2-ol (isopropanol) to propanone (acetone), was not significantly modified by changes in the concentration of the starting TiCl₄. The possibility that the relatively low area of most rutiles contributes to the reported photocatalytic activity of rutile being lower than that of anatase is discussed.     

Photocatalytic activity of Li-Rb-Y doped or codoped TiO2 under sunlight irradiation

Doped TiO₂ particles were synthesized by solid grinding and sol-gel methods. The ensuing powders were analysed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ground state diffuse reflectance absorption spectroscopy (GSDR). The doped samples prepared by solid grinding at 400 °C were in the anatase form, while those synthesised via sol-gel method and calcinated at the same temperature were dominated by the rutile phase. The X-ray photoelectron spectroscopy (XPS) revealed a surface segregation of the doping elements namely for Y, Rb and Rb-Y. The photocatalytic activity of the prepared catalysts, under sunlight irradiation, was evaluated using 2-naphthol as a pollutant model. Results showed a great enhancement in the photocatalytic efficiency with incorporation of Y in samples prepared by solid grinding, while in samples prepared via sol-gel process both Rb and Y dopants greatly improve the photocatalytic activity. The Langmuir-Hinshelwood model was used to describe the photocatalytic reactions from which a pseudo-first-order kinetics was established. The repeatability of photocatalytic activity was also tested for several degradation cycles.     

Synthesis and photocatalytic property of porous TiO2 microspheres

Porous TiO₂ microspheres were prepared in air atmosphere using sol-gel-adding electrolyte method, which is simple and reproducible. The TEM image shows that the diameter of microspheres is around 550 nm. BET measurement indicates that TiO₂ microspheres are of high specific surface area and have a uniform pore size distribution with a mean pore size of 4.4 nm. The pores of the TiO₂ microspheres are monodispersive, mesoporous and interconnecting. XRD shows that calcination at 500 °C transformed the TiO₂ microspheres from amorphous to anatase phase. The degradation experiment demonstrates that the photocatalytic activity of TiO₂ microspheres toward methylene blue dye photodegradation is more efficient than that of the commercial TiO₂ powder. Moreover, the microspheres can be easily removed from the treated solution.     

The effect of the H2 flow rate on the structure and optical properties of TiO2 films deposited by inductively coupled plasma assisted chemical vapor deposition

The optical and photocatalytic properties of TiO₂ are closely related to crystalline structures, such as rutile and anatase. In this paper, TiO₂ films were produced by inductively coupled plasma (ICP) assisted chemical vapor deposition (CVD) without extra heating of the substrate, and the effect of H₂ addition on the structure and optical properties of the films was investigated. After increasing the partial pressure of H₂, the structure of the TiO₂ films changed from anatase to rutile, which usually appears at high temperatures (> 600 °C). The light transmittance decreased with increasing the H₂ flow rate due to the increased surface roughness. The photocatalytic activity of the anatase TiO₂ film was better than that of the rutile TiO₂ film.