Preparation and characterization of TiO2–SiO2 nano-composite thin films

TiO₂ nanocrystalline particles dispersed in SiO₂ have been prepared by the sol-gel method using titanium- and silicon-alkoxides as precursors. Nano-composite thin films were formed on the glass substrates by dip-coating technique and heat treated at temperatures up to 500 °C for 1 h. The size of the TiO₂ nanocrystalline particles in the TiO₂–SiO₂ solution ranged from 5 to 8 nm. The crystalline structure of TiO₂ powders was identified as the anatase phase. As the content of SiO₂ increased, the anatase phase tended to be stabilized to higher temperature. TEM results revealed the presence of spherical TiO₂ particles dispersed in a disk-shaped glassy matrix. Photocatalytic activity of the TiO₂–SiO₂ (1:1) thin films showed decomposition of 95% of methylene blue solution in 2 h and a contact angle of 10°. The photocatalytic decomposition of methylene blue increased and the contact angle decreased with the content of TiO₂ phase. TiO₂–SiO₂ with the molar ratio of 1:1 showed a reasonable combination of adhesion, film strength, and the photocatalytic activity.     

Preparation and characterization of surface bond-conjugated TiO2/SiO2 and photocatalysis for azo dyes

Surface bond-conjugated TiO₂/SiO₂ was prepared by means of the impregnation method. Based on the results of XRD, FTIR, XPS and BET measurements, the growth of titania (predominantly anatase) on the silica substrate seems to occur by anchoring of the TiO₂ phase through Ti–O–Si cross-linking bonds. The structure model of TiO₂/SiO₂ was proposed. Compared to B–TiO₂, the most efficient catalyst is 30 wt.% TiO₂/SiO₂ (Ims30), which showed three times higher photoactivity for the degradation of reactive 15 (R15). In addition, the catalyst had a higher photoactivity on a silica of smaller particle size than on the silica of larger particles. Silica gel plays the basic role of dispersion and support for power TiO₂. The isoelectric point of the catalyst was 3.0 pH units by the measurement of zeta-potential, indicating the presence of the surface acidity of the catalyst. The photodegradation and the adsorption of R15 and cationic blue X-GRL (CBX) were investigated with the change of initial aqueous pH.     

Mesostructured SiO2-doped TiO2 with enhanced thermal stability prepared by a soft-templating sol–gel route

Mesostructured SiO₂–TiO₂ mixed oxides have been prepared by a soft-templating sol–gel route, using a non-ionic triblock copolymer as structure-directing agent. Tetraethylorthosilicate (TEOS) and titanium tetraisopropoxide (TTIP) have been employed as Si and Ti sources, respectively. Using a prehydrolysis TEOS step allows mixed oxides to be produced with a homogeneous porosity and with no phase segregation, in a wide range of Si/Ti compositions. Both the hydrolysis molar ratio and the silicon content have been found to be important factors determining the final properties of these materials. For instance, mixed oxides containing low silicon concentrations exhibit N₂ physisorption isotherms typical of mesoporous materials, although with an important contribution of microporosity. On the other hand, increasing the hydrolysis molar ratio makes more difficult to reach a total dispersion of SiO₂ through the TiO₂ matrix. Even with low SiO₂ loadings, the thermal stability is effectively enhanced, when compared to the equivalent pure TiO₂ materials, as a consequence of a delay in the titania crystallization to anatase. Thus, after calcination at 300 °C for 3 h, mixed oxides containing low Si/Ti ratios (20/80) show BET surface area in the range 290–346 m²/g, while pure TiO₂ materials largely collapse under the same treatment and their BET surface area drop strongly to values around 125 m²/g. This synthesis route, therefore, provides mesoporous TiO₂-rich materials with enhanced stability and textural properties, which is of high interest for applications as catalysts and supports.     

Local structure and photocatalytic activity of B2O3–SiO2/TiO2 ternary mixed oxides prepared by sol–gel method

The local structure and the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides (SiO₂ content was fixed as 30 at.% with respect to TiO₂) was investigated by using XRD, FT-IR, BET, UV-vis spectra, and electron paramagnetic resonance (EPR) measurement. In FT-IR analysis, boron was incorporated into the framework of titania matrix with replacing Ti---O---Si with Si---O---B or Ti---O---B bonds. Also, paramagnetic species such as O⁻ and Ti³⁺ defects were formed by the boron incorporation. In SiO₂/TiO₂ mixed oxides, a blue shift in the light absorption band was observed due to the quantization of band structure. All B₂O₃–SiO₂/TiO₂ samples had pure anatase phase and no rutile phase was formed even though the calcination temperature was over 900 °C. Incorporating boron oxides of more than 10% enlarges the grain size of anatase phase and causes a red shift of the light absorption spectrum. The surface area was monotonically decreased with increasing the content of boron content. As a result, the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides was greatly influenced by the content of boron oxide. The highest photoactivity (g moles/min l) was obtained when the boron content was 5% and seven times higher than that of silica/titania binary mixed oxide. In addition, the specific photoactivity (g moles/m² l) was maximum still at 5%. It was concluded that the large reduction of surface area, the change of band structure, and more formation of bulk Ti³⁺ sites are responsible for the deterioration in the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides when the content of boron is over 10%, although their crystallinity was enhanced by increasing the calcination temperature with keeping anatase phase.     

Hydrogen sorption of magnesium hydride doped with nano-sized TiO2

Various phases of TiO₂ such as anatase, rutile and commercial P25 were added to magnesium hydride by high-energy ball milling in order to improve the hydriding properties of the magnesium. After 1 h milling, the sample containing nano-size rutile powder (200–400 nm) showed uniform distribution, while other shapes of TiO₂ added samples did in separate phase. The effect of the rutile concentrations (3, 5, 7 and 10 mol%) on the hydrogen sorption property of MgH₂ has been investigated and found that the sample containing 5 mol% rutile had the highest hydrogen capacity of 4.40 wt.% at 300 °C and 3.54 wt.% at 250 °C. This amount of hydrogen absorption is still lower than the pure magnesium requires a long activation time, however, its kinetics of hydrogen sorption was greatly enhanced. Moreover, hydrogen absorption capacity was slightly increased with the increase in number of cycles. The mechanism of catalytic effect of uniformly distributed TiO₂ and TiO₂ dispersed as discrete particles in magnesium matrix has been discussed based on microstructural observations.     

Effect of promoters including tungsten and barium on the thermal stability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3

The effect of tungsten and barium on the thermal stability of V₂O₅/TiO₂ catalyst for NO reduction by NH₃ was examined over a fixed bed flow reactor system. The activity of V₂O₅/sulfated TiO₂ catalyst gradually decreased with respect to the thermal aging time at 600 °C. The addition of tungsten to the catalyst surface significantly enhanced the thermal stability of V₂O₅ catalyst supported on sulfated TiO₂. On the basis of Raman and XRD measurements, the tungsten on the catalyst surface was identified as suppressing the progressive transformation of monomeric vanadyl species into crystalline V₂O₅ and of anatase into rutile phase of TiO₂. However, the NO removal activity of V₂O₅/sulfated TiO₂ catalyst including barium markedly decreased after a short aging time, 6 h at 600 °C. This may be due to the transformation of vanadium species to inactive V–O–Ba compound by the interaction with BaO which was formed by the decomposition of BaSO₄ on the catalyst surface at high reaction temperature of 600 °C. The addition of SO₂ to the feed gas stream could partly restore the NO removal activity of thermally aged V₂O₅/sulfated TiO₂ catalyst containing barium.     

Fabrication and characterization of Ag–TiO2 multiphase nanocomposite thin films with enhanced photocatalytic activity

Ag–TiO₂ multiphase nanocomposite thin films were prepared on quartz substrates by the liquid phase deposition (LPD) method from a mixed aqueous solution of ammonium hexafluouotitanate, silver nitrate and boric acid under ambient temperature and atmosphere followed by calcination at 500 °C for 1 h. The grain growth of anatase was depressed upon Ag⁺ doping. However, silver ions not only promoted (or catalyzed) the formation of brookite phase but also reduced the phase transformation temperature of anatase to rutile. With increasing AgNO₃ concentration, the transmittance and band gap of the composite thin films decreased; however, the intensity of surface plasmon absorption (SPA) peaks increased and their peak position shifted to a longer wavelength range. When AgNO₃ concentration was higher than 0.03 M, the prepared samples consisted of anatase, brookite, rutile and metal silver nanocrystal particles, and their grain size ranges were 5–30 nm. The photocatalytic activity of the Ag–TiO₂ multiphase nanocrystal composite thin films prepared by this method exceeded that of pure TiO₂ thin films by a factor of more than 6.3 when AgNO₃ concentration was kept in the range of 0.03–0.05. This was attributed to the fact that there were many hetero-junctions, such as anatase/rutile, anatase/brookite, Ag/anatase, Ag/rutile and so on, existed in the Ag–TiO₂ multiphase nanocomposite films.     

Preparations and photocatalytic properties of magnetically separable nitrogen-doped TiO2 supported on nickel ferrite

A magnetically separable nitrogen-doped photocatalyst TiO_2−xN_x/SiO₂/NiFe₂O₄ (TSN) with a typical ferromagnetic hysteresis was prepared by a simple process: the magnetic SiO₂/NiFe₂O₄ (SN) dispersion prepared by a liquid catalytic phase transformation method and the visible-light-active photocatalyst TiO_2−xN_x were mixed, sonificated, dried, and calcined at 400 °C. The prepared photocatalyst is photoactive under visible light irradiation and easy to be separated from a slurry-type photoreactor under the application of an external magnetic field, being one of promising photocatalysts for wastewater treatment. Transmission electron microscope (TEM) and X-ray diffractometer (XRD) were used to characterize the structure of the TSN photocatalyst. The results indicate that the magnetic SiO₂/NiFe₂O₄ (SN) nanoparticles adhere to the surface of TiO_2−xN_x congeries. The magnetic photocatalyst TSN shows high catalytic activity for the degradation of methyl orange in water under UV and visible light irradiation (λ > 400 nm). SiO₂ coating round the surface of NiFe₂O₄ nanoparticles prevents effectively the injection of charges from TiO₂ particles to NiFe₂O₄, which gives rise to the increase in photocatalytic activity. Moreover, the recycled TSN exhibits a good repeatability of the photocatalytic activity.     

Synthesis of Ti-containing SBA-15 materials and studies on their photocatalytic decomposition of orange II

Titanium substituted SBA-15 mesoporous materials have been successfully prepared by conventional hydrothermal method and they were also used as support on TiO₂ loaded SBA-15 photocatalysts. The synthesized materials were characterized by XRD, UV–vis DRS, FT-IR, BET and TEM. We also examined the activity of these materials as photocatalysts for the decomposition of orange II. The incorporation of titanium into framework of SBA-15 makes the pore diameter and pore volume to decrease and slightly decreases the surface area compared to SBA-15. In addition, the pore size distribution becomes broaden with an increase of titanium amount in the SBA-15 framework. For Ti-SBA-15 and TiO₂ loaded Ti-SBA-15 photocatalysts, the IR absorption at 960 cm⁻¹ commonly accepted the characteristic vibration of Ti–O–Si bond. From the TEM images, the regular silica morphology is maintained in the case of Ti-SBA-15(Si/Ti = 50) but the Ti-SBA-15 sample having Si/Ti ratio = 10 partially destroys the hexagonal highly ordered structure and the mesopore structure is disappeared by the clogging of mesopore channels by the titanium dioxides particles for the 50 wt.% TiO₂/Ti-SBA-15 samples. The photocatalytic activity increases with an increase of Ti content (decrease of Si/Ti ratio) and with an increase of TiO₂ loading content.     

Synthesis of functionalized mesoporous TiO2 molecular sieves and their application in photocatalysis

Functionalized mesoporous TiO₂ molecular sieves were prepared by treating ordered mesoporous TiO₂ with phosphoric acid or ammonium sulfate at high temperature. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption–desorption measurement, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectrometer (FT-IR). The photocatalytic activity of the samples was evaluated by photocatalytic decomposition of bromomethane (CH₃Br) in air. Results revealed that the functionalized TiO₂ samples preserved ordered mesostructure and exhibited enhanced physicochemical properties. The photocatalytic activity of the functionalized mesoporous TiO₂ sample was about three times higher than that of the pure mesoporous TiO₂. The concentrations of phosphoric acid and ammonium sulfate solutions used for the functionalization of TiO₂ greatly influenced the photocatalytic activity of the resultants materials. The optimal concentrations of phosphoric acid and ammonium sulfate solutions were 0.05 and 0.10 M, respectively. The enhanced photocatalytic performance of the functionalized mesoporous TiO₂ could be attributed to large specific surface area, high hydroxyl density, and enhanced surface chemical state.     

Photocatalytic activity and OH radical formation on TiO2 in the relation to crystallinity

Two types of TiO₂ samples, ST-01 (Ishihara-Sangyo, Japan) and A11 precursor (Police, Poland), were heat-treated at 400–1000 °C and characterized by the phase composition, crystallite size and lattice strain. These TiO₂ samples were tested for methylene blue (MB) decomposition and OH radical formation. Through heating TiO₂ up to 700 °C for 1 h the single anatase phase was remained, which had improved crystallinity, large crystallite size and very small lattice strain. By extending the calcination time up to 2–5 h, the anatase phase partially transformed to rutile phase, much faster by A11 precursor than by ST-01. Transformation of anatase phase to rutile reduced the rate of methylene blue decomposition, although OH radical formation was the highest in the samples having around 9 mass% of rutile. However, methylene blue decomposition not only depended on OH radical formation on TiO₂ particles, but also the content of even small amount of rutile in TiO₂ reduces markedly the rate of methylene blue decomposition.     

TiO2-SiO2 and V2O5/TiO2-SiO2 catalyst: Physico-chemical characteristics and catalytic behavior in selective catalytic reduction of NO by NH3

TiO₂-SiO₂ with various compositions prepared by the coprecipitation method and vanadia loaded on TiO₂-SiO₂ were investigated with respect to their physico-chemical characteristics and catalytic behavior in SCR of NO by NH₃ and in the undesired oxidation of SO₂ to SO₃, using BET, XRD, XPS, NH₃-TPD, acidity measurement by the titration method and activity test. TiO₂-SiO₂, compared with pure TiO₂, exhibits a remarkably stronger acidity, a higher BET surface area, a lower crystallinity of anatase titania and results in allowing a good thermal stability and a higher vanadia dispersion on the support up to high loadings of 15 wt% V₂O₅. The SCR activity and N₂ selectivity are found to be more excellent over vanadia loaded on TiO₂-SiO₂ with 10–20 mol% of SiO₂ than over that on pure TiO₂, and this is considered to be associated with highly dispersed vanadia on the supports and large amounts of NH₃ adsorbed on the catalysts. With increasing SiO₂ content, the remarkable activity decrease in the oxidation of SO₂ to SO₃, favorable for industrial SCR catalysts, was also observed, strongly depending on the existence of vanadium species of the oxidation state close to V⁴⁺ on TiO₂-SiO₂, while V⁵⁺ exists on TiO₂, according to XPS. It is concluded that vanadia loaded on Ti-rich TiO₂-SiO₂ with low SiO₂ content is suitable as SCR catalysts for sulfur-containing exhaust gases due to showing not only the excellent de-NO_x activity but also the low SO₂ oxidation performance.     

Characterization and photocatalytic activity of N-doped TiO2 prepared by thermal decomposition of Ti–melamine complex

Nitrogen doped spherical TiO₂ has been prepared by thermal decomposition of Ti–melamine complex in air atmosphere. A clear shift in the onset light absorption from UV region (<400) to visible region (>520 nm) has been observed for the N-doped samples. It has been deduced from the optical absorption spectra that the higher calcination temperature results in the decrease in the amount of N-doping. The XRD results revealed the phase transition of TiO₂ from anatase to rutile crystalline phase, starting at calcination temperature ≥600 °C. The electron microscopic images reveal the formation of spherical and flakes of TiO₂ nanocrystals (25 nm). The chemical nature of N in the N-TiO₂ has been evolved through X-ray photoelectron spectroscopy. The presence of different types of N species have been observed corresponding to different oxidation states and the presence of Ti–N and O–Ti–N have been confirmed from the observed binding energy values. Photocatalytic decomposition of methylene blue has been carried out both in the visible region and UV + visible region. In the visible region, N-TiO₂ showed higher activity compared to the undoped commercial TiO₂ (Degussa P25).     

Effects of hydrothermal temperature and time on the photocatalytic activity and microstructures of bimodal mesoporous TiO2 powders

Bimodal nanocrystalline mesoporous TiO₂ powders with high photocatalytic activity were prepared by a hydrothermal method using tetrabutylorthotitanate (TiO(C₄H₉)₄, TBOT) as precursor. The as-prepared TiO₂ powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and N₂ adsorption–desorption measurements. The photocatalytic activity of the as-prepared TiO₂ powders was evaluated by the photocatalytic degradation of acetone (CH₃COCH₃) under UV-light irradiation at room temperature in air. The effects of hydrothermal temperature and time on the microstructures and photocatalytic activity of the TiO₂ powders were investigated and discussed. It was found that hydrothermal treatment enhanced the phase transformation of the TiO₂ powders from amorphous to anatase and crystallization of anatase. All TiO₂ powders after hydrothermal treatment showed bimodal pore-size distributions in the mesoporous region: one was intra-aggregated pores with maximum pore diameters of ca. 4–8 nm and the other with inter-aggregated pores with maximum pore diameters of ca. 45–50 nm. With increasing hydrothermal temperature and time, the average crystallite size and average pore size increased, in contrast, the Brunauer-Emmett-Teller (BET) specific surface areas, pore volumes and porosity steadily decreased. An optimal hydrothermal condition (180 °C for 10 h) was determined. The photocatalytic activity of the prepared TiO₂ powders under optimal hydrothermal conditions was more than three times higher than that of Degussa P25.     

Photoresponse and AC impedance characterization of TiO2–SiO2 mixed oxide for photocatalytic water decomposition

TiO₂–SiO₂ mixed oxides were prepared by sol–gel processes with one-stage (mix up fully hydrolyzed titania- and silica-sol), two-stage (with pre-hydrolysis) and modified two-stage synthesis routes. The photoresponse and AC impedance characterization of the derived catalysts are studied and correlated for the first time with the photocatalytic activities in water decomposition under UV illumination. Synergistic effects in terms of photocatalytic activity and electronic properties including band-gap energy, flat band potential and doping density were observed on atomically mixing TiO₂ and SiO₂ by the two-stage synthesis route. Meanwhile, the decline of photocurrent density were found on TiO₂–SiO₂ relative to bare TiO₂, which could be attributed to low quality crystalline structure of the former compared to that of the latter. The superior photocatalytic performance of TiO₂–SiO₂ is ascribed to the higher flat band potential, band-gap energy, and doping density than those of bare TiO₂.     

Effect of HCl concentration and reaction time on the change in the crystalline state of TiO2 prepared from aqueous TiCl4 solution by precipitation

TiO₂ powder with 50% by volume or more of brookite phase was obtained by heating aqueous TiCl₄ solution, whose final concentration of HCl after reaction was kept between 4.9 and 6.4 M, at 80 °C for 15 h. Rutile-type TiO₂ was obtained at 5 h of reaction time, a mixture of predominant brookite and rutile at 10–15 h while rutile phase was formed at 25 h. Brookite phase was transformed directly to rutile phase with increase of reaction time but to rutile via anatase phase through heat treatment.     

Photoactivity of anatase–rutile TiO2 nanocrystalline mixtures obtained by heat treatment of homogeneously precipitated anatase

Nanosized titanium dioxide photocatalysts with varying amount of anatase and rutile phases have been synthesized. Homogeneous precipitation of aqueous solutions containing TiOSO₄ with urea was used to prepare porous spherical clusters of anatase TiO_2. Photoactive titania powders with variable amount of anatase and rutile phases were prepared by heating of pure anatase in the temperatutre range 800–1150 °C. The structure evolution during heating of the starting anatase powders was studied by XRD analysis in overall temperature range of phase transformation. The morphology and microstucture characteristics were also obtained by HRTEM, BET and BJH. The spherical particle morphology of TiO₂ mixtures determined by SEM was stable in air up to 900 °C. The photocatalytic activity of the sample titania TIT85/825 heated to 825 °C in air, contained 77.4% anatase and 22.6% rutile was higher than that nanocrystalline anatase powder. Titania sample TIT85/825 reveals the highest catalytic activity during the photocatalyzed degradation of 4-chlorophenol in aqueous suspension.     

Synthesis of TiO2 particles by reverse microemulsion method using nonionic surfactants with different hydrophilic and hydrophobic group and their photocatalytic activity

TiO₂ nanoparticles were prepared using hydrolysis of titanium tetraisopropoxide in W/O microemulsions consisting of water, nonionic Brij series surfactants with different hydrophilic and Tween series surfactants with different hydrophobic group, and cyclohexane. The properties of these particles were characterized by TEM, XRD, FT-IR, TGA and DTA. The photocatalytic degradation of p-nitrophenol has been studied in order to compare the photocatalytic activity of prepared nanosized titania. TiO₂ particles calcined at 500 °C have a stable anatase phase which has no organic surfactants and the product completely transforms into the anatase phase above 300 °C and the rutile phase begins to appear at 600 °C regardless of surfactants. The particles are shown to have a spherical shape and have an uniform size distribution but the shape becomes distorted with a decrease of hydrophilic group chain length according to rapid hydrolysis of water and titanium alkoxide. In addition, the crystallite size and crystallinity increase with a decrease of hydrophilic and hydrophobic group chain length and an increase of calcination temperature. The photocatalytic activity increases with an increase of hydrophilic and hydrophobic group length and the titania calcined at 500 °C shows the highest activity on the photocatalytic degradation of p-nitrophenol regardless of surfactants.     

铈硅包覆金红石型钛白粉及光催化性研究

采用溶胶-凝胶法,制备了铈硅包覆金红石型钛白粉,通过正交实验考察了浆液浓度、分散剂用量和两种包膜剂含量对铈硅包覆金红石型钛白粉性能的影响。采用Nano-ZS型粒度仪、扫描电镜（SEM）、透射电镜（TEM）和能谱（EDS）等测试手段,对金红石型钛白粉的Zeta电位、表面形貌和元素进行了表征。结果表明：在水浴温度为80 ℃左右、转速为600 r/min、浆液质量浓度为400 g/L、分散剂质量分数为0.1%、二氧化铈质量分数为3%、二氧化硅质量分数为4%的条件下,金红石型钛白粉表面包覆了两层均匀而致密的二氧化硅和二氧化铈膜;罗丹明B光催化降解实验证实,铈硅包覆明显改善了金红石型钛白粉的光催化屏蔽性。     

Carbon-modified TiO2 photocatalyst by ethanol carbonisation

The new photocatalysts based on commercially available titanium dioxide powders: Tytanpol A11 (Police, Poland), pure anatase and P-25 (Degussa, Germany) containing about 20% rutile were modified by carbon via ethanol carbonisation. Titanium dioxides were heated at different temperature from 150 to 400 °C for 1 h in an atmosphere of ethanol vapour. The photocatalytic activity of carbon-modified TiO₂ was studied by oxidation of phenol in water under UV and artificial solar light irradiation. With increasing of carbon content in TiO₂ photocatalysts the activity for phenol decomposition under UV light was decreasing but that under visible light was stable. Turbidity of the slurry solution decreased with increasing of carbon content for all prepared photocatalysts because of the change of their surface character from hydrophilic to hydrophobic.