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.     

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.     

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.     

硅藻土负载La~(3+)/TiO_2光催化剂的制备及其光催化性能

以钛酸四丁酯为前驱体,硅藻土为载体,采用溶胶-凝胶法制备TiO_2/硅藻土负载型光催化剂。以硝酸镧为镧源,采用等体积浸渍-焙烧法制备La~(3+)/TiO_2硅藻土光催化剂。通过XRD和SEM对制备的催化剂进行表征,以亚甲基蓝溶液模拟有机废水,考察n(Ti)∶n(Si)及La3+掺杂量对催化剂光催化性能的影响,结果表明,硅藻土可提高TiO_2分散性,降低TiO_2晶粒尺寸,并抑制其由锐钛矿相向金红石相的转变。在n(Ti)∶n(Si)=1∶1、焙烧温度550℃和La3+掺杂质量分数1%条件下,La~(3+)/TiO_2硅藻土光催化剂的光催化活性较好,紫外光连续照射180 min,亚甲基蓝降解率可达99.9%。     

Influence of the surface area of the support on the activity of gold catalysts for CO oxidation

In the preparation of 1% Au/TiO₂ catalysts supported on either Degussa P-25 or anatase (90 m² g⁻¹) by deposition–precipitation, the gold content passes through a maximum at about the isoelectric point (pH 6), but maximum specific rates occur at pH 8–9 because the Au particle size becomes smaller as the pH is further increased. The gold uptake increases with the surface area of the support (anatase, rutile, P-25) and is complete above 200 m² g⁻¹; adsorption of the gold precursor at pH 9 is shown to be equilibrium-limited. Highest activities are found with supports of 50 m² g⁻¹. Catalysts made with high-area anatase (240 or 305 m² g⁻¹) are least active but show least deactivation.With Au/SnO₂ catalysts, gold uptake does not depend on the area of the support, and is highest at pH 7–8; very active catalysts (T₅₀ = 230–238 K) are obtained using SnO₂ of 47 m² g⁻¹. Storing a catalyst at 258 K for 1 week dramatically improves its stability. Results for Au/CeO₂ and Au/ZrO₂ catalysts confirm that moderate support areas give the most active catalysts, and suggest that surface area is often more important than chemical composition.     

Effect of sulfate ions for sol–gel synthesis of titania photocatalyst

We have found that the use of sulfuric acid in the peptization process of sol–gel method produced SO₄²⁻-incorporated TiO₂ which is mechanically strong by firing at low temperature such as 200°C. The synthesized TiO₂ has larger specific surface area and retards the phase transition from anatase to rutile compared with that prepared from the peptization with nitric acid. The S-content of the TiO₂ fired at 200°C was 1.52 wt.%; the value has a maximum of 2.74 wt.% at 400°C. The XPS measurements indicate that S exists mainly as SO₄²⁻. The TiO₂ fired at 400°C showed the highest photocatalytic activity for ethylene degradation. Especially, we would like to emphasize the TiO₂ sintered at 200°C because they are extremely hard in spite of such a low sintering temperature. This photocatalyst may provide a great opportunity for extensive applications as self-supporting membranes.     

Synthesis of nanosized TiO2/SiO2 particles in the microemulsion and their photocatalytic activity on the decomposition of p-nitrophenol

Nanosized pure TiO₂ particles were prepared by hydrolysis of TTIP in the sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. TiO₂/SiO₂ nanoparticles were also prepared from TEOS as a silicon source and TTIP as a titanium source. These particles were characterized by TEM, XRD, FT-IR, BET, TGA and DTA. From thermal analysis and XRD analysis, the anatase structure of pure titania appeared in the 300–600 °C calcination temperature range and the rutile structure was showed above 700 °C. However, no rutile phase was observed for the TiO₂/SiO₂ particles up to 800 °C. The crystallite size decreased and the surface area of TiO₂/SiO₂ particles monotonically increased with an increase of the silica content. From FT-IR analysis, the band for Ti–O–Si vibration was observed and the band intensity for Si–O–Si vibration increased with an increase of the silica content. The micrographs of TEM showed that the TiO₂/SiO₂ nanoparticles had a spherical and a narrow size distribution. In addition, TiO₂/SiO₂ particles showed higher photocatalytic activity than pure TiO₂ and the TiO₂/SiO₂ (90/10) particles showed the highest activity on the photocatalytic decomposition of p-nitrophenol.     

On the modification of photocatalysts for improving visible light and UV degradation of gas-phase toluene over TiO2

The photocatalytic behavior of different TiO₂-based photocatalysts was reported for gas-phase toluene removal under both UV and visible light illumination, and compared to that of commercial P25 (Degussa) TiO₂. Promotion by sulfates and the use of nanosized anatase TiO₂ were reported to strongly increase the toluene removal efficiency under UV illumination. Nanosized-anatase was prepared by a protecting group sol–gel synthesis using hexamethyldisilazane as crystallite growth inhibitor. Sulfates played a double positive role, with photogenerated electrons transfer effects limiting charge recombination and as repulsive species for strongly adsorbed aromatic intermediates that act as poisons. The decrease in particle size obtained on nanosized anatase TiO₂ (5 nm) yielded a considerable enhancement in the toluene removal efficiency. Pure high surface area rutile has been synthesized at low temperature by a polyethylenglycol-containing sol–gel method for visible light activation purposes. A two-way semiconductor coupling phenomenon, consisting of a reciprocal electron/hole transfer between two visible light-activated oxides, rutile TiO₂ and WO₃, was proposed to explain the large gain in efficiency when adding low amounts of WO₃ to rutile TiO₂.     

Facile synthesis and enhanced visible-light photocatalytic activity of Ti3+-doped TiO2 sheets with tunable phase composition? ?

Ti³⁺-doped TiO₂ nanosheets with tunable phase composition (doped TiO₂ (A/R)) were synthesized via a hydrothermal method with high surface area anatase TiO₂ nanosheets TiO₂ (A) as a substrate, structure directing agent, and inhibitor; the activity was evaluated using a probe reaction-photocatalytic CO₂ conversion to methane under visible light irradiation with H₂ as an electron donor and hydrogen source. High-resolution transmission electron microscope (HRTEM), field emission scanning electron microscope, UV-Vis diffuse reflectance spectra, and X-ray diffraction (XRD) etc., were used to characterize the photocatalysts. XRD and HRTEM measurements confirmed the existence of anatase-rutile phase junction, while Ti³⁺ and single-electron-trapped oxygen vacancy in the doped TiO₂ (A/R) photocatalyst were revealed byelectron paramagnetic resonance (EPR) measurements. Effects of hydrothermal synthesis temperature and the amount of added anatase TiO₂ on the photocatalytic activity were elucidated. Significantly enhanced photocatalytic activity of doped TiO₂ (A/R) was observed; under the optimized synthesis conditions, CH₄ generation rate of doped TiO₂ (A/R) was 2.3 times that of Ti³⁺-doped rutile TiO₂.     

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.     

A comparative study of TiO2 supported noble metal catalysts for the oxidation of formaldehyde at room temperature

The TiO₂ supported noble metal (Au, Rh, Pd and Pt) catalysts were prepared by impregnation method and characterized by means of X-ray diffraction (XRD) and BET. These catalysts were tested for the catalytic oxidation of formaldehyde (HCHO). It was found that the order of activity was Pt/TiO₂  Rh/TiO₂ > Pd/TiO₂ > Au/TiO₂  TiO₂. HCHO could be completely oxidized into CO₂ and H₂O over Pt/TiO₂ in a gas hourly space velocity (GHSV) of 50,000 h⁻¹ even at room temperature. In contrast, the other catalysts were much less effective for HCHO oxidation at the same reaction conditions. HCHO conversion to CO₂ was only 20% over the Rh/TiO₂ at 20 °C. The Pd/TiO₂ and Au/TiO₂ showed no activities for HCHO oxidation at 20 °C. The different activities of the noble metals for HCHO oxidation were studied with respect to the behavior of adsorbed species on the catalysts surface at room temperature using in situ DRIFTS. The results show that the activities of the TiO₂ supported Pt, Rh, Pd and Au catalysts for HCHO oxidation are closely related to their capacities for the formation of formate species and the formate decomposition into CO species. Based on in situ DRIFTS studies, a simplified reaction scheme of HCHO oxidation was also proposed.     

超临界干燥法制备TiO2/凹凸棒复合光催化剂

以凹凸棒为载体,四氯化钛为钛源,通过溶胶-凝胶法结合超临界干燥法制备TiO₂/凹凸棒复合光催化材料。采用XRD、SEM、TEM、BET、XPS等方法对材料的结构、形貌及催化性能进行表征。研究结果表明：超临界干燥可增大复合材料的比表面积,抑制TiO₂发生晶型转变。凹凸棒吸附特性良好,增加了材料表面的活性位点,显著提高催化剂的光催化活性。不同煅烧温度下的TiO₂均为锐钛矿型,粒径约为20 nm,呈不规则短棒状,成功负载于凹凸棒上。在400℃煅烧2 h条件下,催化剂3 h后对亚甲基蓝的降解率可达98.4%。     

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.     

Formation of active state in vanadium–titanium oxide system regarding to reaction of oxidation of β-picoline to nicotinic acid

Binary vanadia–titania catalysts comprising 5–75 wt.% of V₂O₅ and 95–25 wt.% of TiO₂, pretreated at the temperature ranging between 300 and 700°C, were studied as heterogeneous catalysts for oxidation of β-picoline at 250°C, and inlet concentrations of the following components (vol.%): 1% of 3-picoline, 20% of oxygen, 30% of steam. Nicotinic acid, 3-pyridinecarbaldehyde and CO₂ were the reaction products. The most active state for oxidation of 3-picoline into nicotinic acid was shown to result from formation of coherent interface between V₂O₅ and TiO₂ (anatase) crystallites. This state was generated at the temperature particular for each composition and persists below the temperature of the anatase to rutile transition.     

Performance and characterization of supported metal catalysts for complete oxidation of formaldehyde at low temperatures

Activities of a series of metals (Pt, Pd, Rh, Cu, Mn) supported on TiO₂ were investigated for the catalytic oxidation of formaldehyde. Among them, Pt/TiO₂ was found to be the most promising catalyst. Nitrogen adsorption, hydrogen chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and temperature programmed reduction (TPR) by H₂ were used to characterize the platinum catalysts. Using Ce_0.8Zr_0.2O₂, Ce_0.2Zr_0.8O₂, SiO₂ as supports instead of TiO₂, the activity sequence of 0.6 wt.% platinum with respect to the supports is TiO₂ > SiO₂ > Ce_0.8Zr_0.2O₂ > Ce_0.2Zr_0.8O₂, and this appears to be correlated with the dispersion of platinum on supports rather than the specific surface areas of the catalysts. Platinum loading on TiO₂ has a great effect on the catalytic activity, and 0.6 wt.% Pt/TiO₂ catalyst was observed to be the most active, which could be attributed to the well-dispersed platinum surface phase. The reduction temperature greatly affects the particle size and, consequently, the catalytic activity. The smaller particle size of platinum, due to its high dispersion on support, has a positive effect on catalytic performance. Increasing formaldehyde concentration and space velocity exhibits an inhibiting effect on the catalytic activity.     

Visible light photocatalysis on praseodymium(III)-nitrate-modified TiO2 prepared by an ultrasound method

Nanocrystalline TiO₂ incorporated with praseodymium(III) nitrate has been prepared by an ultrasound method in a sol–gel process. The prepared sample is characterized by X-ray diffraction (XRD), nitrogen adsorption (BET surface area), UV–vis diffuse reflectance spectroscopy (UV–Vis DRS) and X-ray photoelectron spectroscopy (XPS). The prepared material consists of TiO₂ nanocrystalline with 5 nm size incorporated with highly dispersed Pr(NO₃)₃. Visible light absorptions at 444, 469, 482 and 590 nm are observed in the prepared sample. These bands are attributed to the 4f transitions ³H₄ → ³P₂, ³H₄ → ³P₁, ³H₄ → ³P₀ and ³H₄ → ¹D₂ of praseodymium(III) ions, respectively. This sample Pr(NO₃)₃-TiO₂, as a novel visible light photocatalyst, shows high activity and stability in the decomposing rhodamine-B (RhB) and 4-chlorophenol (4-CP) under visible light irradiation. Results examined by electron spin resonance spectroscopy (ESR) reveal that the irradiation (>420 nm) of the photocatalyst dispersed in RhB aqueous solution induces the generation of highly active hydroxyl radicals (OH), leading to the cleavage of the whole conjugated chromophore structure of RhB. A mechanism based on local excitation of praseodymium(III) nitrate chromophore and interfacial charge transfer from the chromophore to TiO₂ is proposed to explain the formation of active hydroxyl radicals in the photocatalytic system under visible light irradiation.     

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.     

Photodegradation of phenol in water using silica-supported titania catalysts

Titania-coated silica microspheres containing 0.5–3.0 theoretical layers of TiO₂ have been prepared by homogeneous precipitation of TiCl₃. All these χ TiO₂-SiO₂ materials were characterized by X-ray diffraction and FT-Raman spectroscopy. TiO₂ species are distributed on the surface as small anatase crystals and possess a titania-like behavior with a performance equivalent to that of bulk TiO₂ for the photodegradation of phenol. The fraction of used titania is higher than that on bulk catalysts and the absorption of the irradiation by excess titania is prevented. The crystal size of titania particles is critical for optimum performance of the catalyst, since it determines the appropriate surface exposure of titanium sites. A minimum size appears to be required to efficiently mineralize phenol.     

Support effects on structure and activity of molybdenum oxide catalysts for the oxidative dehydrogenation of ethane

The structural and catalytic properties of MoO₃ catalysts supported on ZrO₂, Al₂O₃, TiO₂ and SiO₂ with Mo surface densities, n_s, in the range of 0.5–18.5 Mo/nm² were studied for the oxidative dehydrogenation (ODH) of ethane by in situ Raman spectroscopy and catalytic activity measurements at temperatures of 400–540 °C. The molecular structure of the dispersed surface species evolves from isolated monomolybdates (MoO₄ and MoO₅, depending on the support) at low loadings to associated MoO_x units in polymolybdate chains at high loadings and ultimately to bulk crystalline phases for loadings exceeding the monolayer coverage of the supports used. The nature of the oxide support material and of the Mo–O–support bond has a significant influence on the catalytic behaviour of the molybdena catalysts with monolayer coverage. The dependence of reactivity on the support follows the order ZrO₂ > Al₂O₃ > TiO₂ > SiO₂. The oxygen site involved in the anchoring Mo–O–support is of relevance for the catalytic activity.