Photocatalysis of methylene blue on titanium dioxide nanoparticles synthesized by modified sol-hydrothermal process of TiCl4

Titanium dioxide nanoparticles were synthesized by the hydrolysis and condensation of TiCl₄, an economic titanium precursor, in a mixed solvent of iso-propyl alcohol and water. As-prepared powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), energy filtering transmission electron microscopy (EF-TEM). To examine the photocatalytic activity of the as-prepared TiO₂, the photodegradation of MB which is a typical dye resistant to biodegradation has been investigated on TiO₂ powders in aqueous heterogeneous suspensions. The photocatalytic activity of TiO₂ powders prepared by the hydrolysis of TiCl₄ in the mixed solutions of iso-PrOH/H₂O exceeded that of commercial TiO₂ powders. The apparent first order rate constants (k _app) for the photodegradation of methylene blue (MB) showed a good correlation with the absorbance area obtained by UV-VIS DRS on wavelength in the limits of used lamp emission 300∼420 nm.     

Enhancing Effects of Ultrasound Treatment on the Preparation of TiO2 Photocatalysts

TiO₂ nanoparticles were synthesized by the hydrolysis and condensation of TiCl₄ in a mixed solvent of iso-propyl alcohol and water with or without ultrasound treatment. As-prepared powders were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy filtering transmission electron microscopy (EF-TEM), particle size analysis and BET surface area analysis. The specific surface area, thermal stability and crystallization of the as-prepared samples treated with ultrasound were higher than those of samples treated without ultrasound. To examine the photocatalytic activity of the as-prepared TiO₂, the photodegradation of MB which is a typical dye resistant to biodegradation has been investigated on TiO₂ powders in aqueous heterogeneous suspensions. The photocatalytic degradation of a aqueous solution of methylene blue shows a remarkable increase when it is carried out with ultrasound in all cases.     

Preparation of TiO2/carbon nanotubes photocatalysts: The influence of the method of oxidation of the carbon nanotubes on the photocatalytic activity of the nanocomposites

A method for the preparation of efficient TiO₂/multi-wall carbon nanotubes nanocomposite photocatalysts by precipitation of anatase TiO₂ nanoparticles onto differently oxidized carbon nanotubes is presented. The precursor compound titanium(IV) bromide was hydrolyzed producing pure anatase phase TiO₂ nanoparticles decorated on the surface of the oxidized carbon nanotubes. The oxidative treatment of the carbon nanotubes influenced the type, quantity and distribution of oxygen-containing functional groups, which had a significant influence on the electron transfer properties, i.e., the photocatalytic activity of the synthesized nanocomposites. The results of C.I. Reactive Orange 16 photodegradation in the presence of all the synthesized nanocomposites showed their better photocatalytic activity in comparison to the commercial photocatalyst Degussa P-25.     

Effects of I and F codoped TiO2 on the photocatalytic degradation of methylene blue

Nanocrystalline I-F-codoped TiO₂ was prepared by a sol-gel-impregnation method, using tetrabutylorthotitanate in a mixed NH₄I-NH₄F aqueous solution. The as-prepared TiO₂ was characterized with UV-vis diffuse reflectance spectra, X-ray diffraction and nitrogen adsorption. The degradation of methylene blue (MB) over as-prepared TiO₂ in aqueous solution under simulated sunlight irradiation was remarkably enhanced by codoping with I and F. The effects of codoping and calcination temperature on the photocatalytic activity and microstructures were investigated. The photocatalytic activity of as-prepared I-F-codoped TiO₂ was remarkably higher than that of pure, I-doped, and F-doped TiO₂ when the molar ratios of I and F to Ti were kept in the value of 10. The influence of I-F-modification on the photocatalytic activity was discussed by considering the higher surface area, entire anatase phase, effective dopant content, and stronger absorbance of sunlight, corresponding to the higher quantum efficiency. In addition to a complete removal of color, the as-prepared TiO₂ was simultaneously able to oxidize MB and small amounts of intermediates such as formic acid and phenol were detected. After prolonged sunlight irradiation some intermediates almost vanished, and MB appeared to be eventually mineralized to NH₄⁺, NO₃⁻ and SO₄²⁻.     

Fabrication of high-efficiency anatase TiO2 photocatalysts using electrospinning with ultra-violet treatment

In metal oxide nanofiber fabrication using the electrospinning method, heat treatment is performed at temperatures of 500°C or higher for crystallization and polymer desorption. Therefore, it is difficult to fabricate low-temperature phase metal oxides that crystallize at low temperatures. TiO₂, a representative metal oxide often used as photocatalysts, is known to have higher photocatalytic activity in the low-temperature phase (anatase structure) than in the high-temperature phase (rutile structure). Studies on the fabrication of TiO₂ anatase nanofibers using conventional electrospinning have reported disadvantages such as the partial expression of rutile structures and low crystallinity. This study developed an anatase TiO₂ nanofiber as a high-efficiency catalyst based on the electrospinning method and a residual organic matter cleaning method that employs ultra-violet (UV) light. We fabricated nanofibers using the electrospinning method and implemented TiO₂ nanofibers with the anatase structure through heat treatment at 260°C. Residual organics remaining after heat treatment of the fabricated crystalized TiO₂ nanofibers were removed by exposing them to UV light, thereby improving photocatalytic efficiency. The photocatalytic efficiency of the fabricated TiO₂ nanofibers was confirmed through a methylene blue (MB) decomposition experiment under visible light irradiation. The photocatalytic efficiency (time taken for the concentration of the MB solution to reach 50%) of the UV-treated TiO₂ nanofibers was approximately six times higher than of P25 and the heat-treated nanofibers.     

In situ synthesis,fabrication and Rietveld refinement of the hydroxyapatite/titania composite coatings on 316 L SS

The development of Hydroxyapatite (HAP)/Titania (TiO₂) composite coatings on metallic implants have received a great deal of attention during the recent years owing to their superior advantages in biomedical applications. The present study has focused on the in situ formation of HAP/TiO₂ composite powders through aqueous precipitation technique. Five different HAP/TiO₂ composite powders of varied HAP to TiO₂ ratios has been synthesized in the present study and the results were compared with the stoichiometric HAP, Rutile TiO₂ and Anatase TiO₂ which also have been synthesized by adapting a similar synthetic procedure. All the synthesized powders have been analyzed using X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Rietveld Refinement technique has been employed to generate quantitative information about the structural characteristics and phase content in all the powder samples. Further, the electrophoretic deposition (EPD) method has been employed to fabricate HAP/TiO₂ composite coatings on 316 L SS and the resultant coatings were analyzed for its quantitative structural characteristics. The results from the present investigation has confirmed that concentration of TiO₂ in the HAP/TiO₂ composites and heat treatment temperatures have played a major role in the degradation of HAP to β-Tricalcium phosphate and also in the conversion of Anatase to Rutile TiO₂ phase.     

Preparation of polyaniline-modified TiO2 nanoparticles and their photocatalytic activity under visible light illumination

Titanium dioxide nanoparticles were modified by polyaniline (PANI) using ‘in situ’ chemical oxidative polymerization method in hydrochloric acid solutions. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy spectrum (XPS) and UV–vis spectra were carried out to characterize the composites with different PANI contents. The photocatalytic degradation of phenol was chosen as a model reaction to evaluate the photocatalytic activities of the modified catalysts. Results show that TiO₂ nanoparticles are deposited by PANI to mitigate TiO₂ particles agglomeration. The modification does not alter the crystalline structure of the TiO₂ nanoparticles according to the X-ray diffraction patterns. UV–vis spectra reveal that PANI-modified TiO₂ composites show stronger absorption than neat TiO₂ under the whole range of visible light. The resulting PANI-modified TiO₂ composites exhibit significantly higher photocatalytic activity than that of neat TiO₂ on degradation of phenol aqueous solution under visible light irradiation (λ ≥ 400 nm). An optimum of the synergetic effect is found for an initial molar ratio of aniline to TiO₂ equal to 1/100.     

Photocatalytic degradation of dyestuff wastewater under visible light irradiation using micron‐sized mixed crystal TiO2 powders

A phase transformation of micron‐sized TiO₂ powder from anatase to rutile was attempted by heat‐treatment in order to generate a new mixed crystal TiO₂ with high associated photocatalytic activity. Heat‐treated micron‐sized TiO₂ powders at different transition stages were characterized by X‐ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT‐IR) and transmission electron microscopy (TEM) methods. The tests of photocatalytic activity of the heat‐treated micron‐sized TiO₂ powders were conducted by the photocatalytic degradation of Rhodamine B and Acid Red B under visible light irradiation. The results indicate that mixed crystal TiO₂ photocatalyst heat‐treated at 400 °C for 60 min shows the highest photocatalytic activity. It can effectively decompose the Rhodamine B and Acid Red B in aqueous solution after 6 h visible light irradiation. A remarkable improvement in photocatalytic activity of TiO₂ is caused by the formation of combined rutile–anatase phases and separation of photogenerated electron–hole pairs. Copyright © 2007 Society of Chemical Industry     

Effect of pre-nitridation treatment on the formation of anatase TiO2 films by anodization

High performance-anatase TiO₂ films were successfully formed on metallic titanium by anodization in an acidic electrolyte composed of H₂SO₄, H₃PO₄ and H₂O₂ subsequent to pre-nitridation treatment. The pre-nitridation treatment was carried out by pre-annealing metallic titanium under a nitrogen atmosphere of 0.1 MPa. The anodized films showed photocatalytic activity in photooxidization of the iodide anion into the tri-iodide anion. The nitridation treatment had a significant effect not only on the formation of anatase TiO₂ films but also on the photocatalytic activity of the anodized films.     

Visible photocatalytic activity and photoelectrochemical behavior of TiO2 nanoparticles modified with metal porphyrins containing hydroxyl group

TiO₂ nanoparticles modified with 5-(p-hydroxylphenyl)-10,15,20-triphenylporphyrin (HTPP), 5-(p-hydroxylphenyl)-10,15,20-triphenylporphyrin zinc (ZnHTPP) and trans-dichloro-5-(p-hydroxylphenyl)-10,15,20-triphenylporphyrin tin (SnHTPP) were prepared in order to improve the visible photocatalytic activity of TiO₂ nanoparticles. The photocatalytic activity of the modified TiO₂ nanoparticles was investigated by carrying out the photodegradation of methyl orange in aqueous solution under visible light irradiation. The TiO₂ nanoparticles modified with SnHTPP show the highest visible photocatalytic activity with a degradation ratio of 86% of methyl orange after 180 min irradiation among three catalysts. This result indicates that the central metal ions in porphyrins can significantly influence the sensitization efficiency of porphyrins. In addition, the photoelectrochemical behavior of the modified TiO₂ nanoparticles was examined and related to their photocatalytic activity. Finally, the photocatalytic mechanism was discussed preliminarily.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Determination of the photocatalytic efficiency of TiO2 coatings on ceramic tiles by monitoring the photodegradation of organic dyes

A method for the evaluation of the photocatalytic effectiveness of nanotitania coatings on ceramic substrate was established. Decolourization of three organic dyes, including methylene blue (MB), rhodamine B (RB) and crystal violet (CV), was investigated under different experimental conditions. The results showed that the UV light spectrum and light intensity are important parameters when establishing this method.The effect of TiO₂ on the percentage degradation of the dyes was examined by varying its concentration in the suspensions between 0.1% and 4.5 wt%, which resulted in different thicknesses of the TiO₂ layers, and as expected higher percentages of nanotitania resulted in higher photocatalytic efficiencies. However higher amounts of titania lead to the formation of cracks on the surface, which might detrimentally affect adhesion and thus also long-term durability. The applicability of all the dyes used in the present study was proved, and there is good correlation between MB, RB and CV in the evaluation of self-cleaning efficiency.     

Microstructure and photocatalytic activity of electrospun carbon nanofibers decorated by TiO2 nanoparticles from hydrothermal reaction/blended spinning

Recently, carbon nanofibers@TiO₂ (CNFs@TiO₂) composites as photocatalysts for dye degradation have attracted intense attention. However, only few contributions had been made to investigate systematically the differences between the various preparation approaches and the influence of thermal treatment on the photocatalytic activity. In this work, the electrospun CNFs@TiO₂ composites which were prepared by hydrothermal reaction and blended spinning, respectively, have been fabricated via stabilization in air at 280 °C and then carbonization in N₂ at heat treatment temperature between 500 and 1100 °C. The composites which were prepared by hydrothermal reaction and blended spinning showed the outstanding photocatalytic activity at 900 °C and 1100 °C, respectively. And the photocatalytic activity of composites prepared by hydrothermal reaction was higher than that prepared by blended spinning, but reversibility of the composites showed a reverse trend. These results indicated that the effect of heat treatment temperature on the photocatalytic activity depended on the synergistic effect among the adsorptive property of CNFs, TiO₂ loading amount and anatase phase content in composites. Hence, combining the merits of hydrothermal reaction and blended spinning, a novel method for preparing CNFs@TiO₂ composites with high TiO₂ loading amount and strong interfacial interaction could be envisioned.     

Photocatalytic activity of TiO2 supported on multi-walled carbon nanotubes under simulated solar irradiation

TiO₂ particles supported on multi-walled carbon nanotubes (MWCNTs) were prepared using a sol–gel method to investigate their photocatalytic activity under simulated solar irradiation for the degradation of methyl orange (MO) in aqueous solution. The prepared composites were analyzed using XRD, SEM, EDS and UV–vis absorption spectroscopy. The results of this study indicated that there was little difference in the shape and structure of MWCNTs/TiO₂ composite and pure TiO₂ particles. The composite exhibited enhanced absorption properties in the visible light range compared to pure TiO₂. The degradation of MO by MWCNTs/TiO₂ composite photocatalysts was investigated under irradiation with simulated solar light. The results of this study indicated that MWCNTs played a significant role in improving photocatalytic performance. Different amounts of MWCNTs had different effects on photodegradation efficiency, and the most efficient MO photodegradation was observed for a 2% MWCNT/TiO₂ mass ratio. Photocatalytic reaction kinetics were described using the Langmuir–Hinshelwood (L–H) model. The photocatalyst was reused for eight cycles, and it retained over 95.2% photocatalytic degradation efficiency. Possible decomposition mechanisms were also discussed. The results of this study indicated that photocatalytic reactions with TiO₂ particles supported on MWCNTs under simulated solar light irradiation are feasible and effective for degrading organic dye pollutants.     

Effect of calcination temperature on the structural properties and photocatalytic activities of solvothermal synthesized TiO2 hollow nanoparticles

TiO₂ hollow nanoparticles were prepared by the solvothermal method, calcined at different temperatures and characterized by XRD, BET, SEM, PL and FT-IR. The effects of morphology, size and calcination temperature on the photocatalytic activity of the prepared materials were discussed in detail. It was found that the calcination temperature altered the crystallinity, morphology, surface area, and the porous structure. The photocatalytic activity of the TiO₂ powders evaluated through photocatalytic degradation of gaseous acetone under UV-light irradiation, showed TiO₂ calcined at 250 °C to exhibit a higher photocatalytic activity than commercial powders (Degussa P25).     

Effect of Mg-and Fe-ions on formation mechanism of aluminium titanate

The presence of Mg²⁺- and Fe³⁺-ions has an effect on the formation of Al₂TiO₅. Crystalline phases produced under the influence of the heat treatment have been identified in a heated X-ray diffraction chamber in the temperature range of 20–1500 °C. In the presence of Mg²⁺- and Fe³⁺-ions transitional phases are formed in the temperature range of 1000–1350 °C during Al₂TiO₅ formation. The XRD technique was used to identify the crystalline phases formed. On addition of MgO, chemical composition of the transitional phase formed is Mg_0.3Al_1.4Ti_1.3O₅, whereas on addition of Fe₂O₃ we have calculated a Powder Diffraction File card data for the transitional phase. Determination of the lattice parameters of the Al₂TiO₅ ceramics produced enabled verification of incorporation of Mg²⁺- or Fe³⁺-ions into the crystal lattice of Al₂TiO₅, i.e. the formation of Mg²⁺- and Fe³⁺-containing solid solutions.     

Carbon coating of anatase-type TiO2 through their precipitation in PVA aqueous solution

Fine particles of photocatalytic anatase-type TiO₂ prepared through hydrolysis of titanium-tetraisopropoxide were coated by carbon through their precipitation in poly(vinyl alcohol) (PVA) aqueous solution, followed by heat treatment at high temperatures of 400-1000 °C in a flow of high purity Ar. Without carbon coating, the phase transformation from anatase to rutile started above 600 °C, but it was suppressed up to 800 °C with carbon coating. Suppression of the phase transformation depended on the amount of carbon coated, apparent suppression being observed with carbon content above 5 mass%. The amount of carbon coated on anatase was controlled by changing the concentration of PVA in the solution. In order to have a carbon content of about 5 mass%, a PVA solution with more than 2 mass% had to be used.     

Investigation of phase separation of nano-crystalline anatase from TiO2SiO2 thin film

In this work, a set of SiO₂–TiO₂ mixed oxides was prepared by the polymeric sol–gel route and deposited on glass substrate through the dip coating technique. Then, the effect of different important preparation parameters (sol–gel stabilizers, Ti content, and heat treatment) on the phase separation was investigated. The developed films were heat treated at 500 °C and characterized using TGA/DTA, FTIR, XRD, SEM, and AFM. The results showed that TiO₂ segregation can be controlled by selecting an appropriate composition of diethanolamine (DEA) and methyl methacrylate (MMA) for preparation of polymeric silica–titania sol. Besides, anatase phase in the samples were crystallized without any stabilizers within heat treatment procedure at 500 °C; however, using appropriate composition of DEA and MMA crystallization rate significantly decreased.     

Enhancement of the photocatalytic reactivity of TiO2 nano-particles by a simple mechanical blending with hydrophobic mordenite (MOR) zeolite

The photocatalytic oxidation of gaseous acetaldehyde with O₂ on commercial TiO₂ nano-particles could be successfully enhanced by a simple mechanical blending with a high-silica mordenite (MOR) zeolite, the surface of which showed high hydrophobic properties. When the TiO₂ nano-particles of ca. 5–20 wt% were mixed with the MOR zeolite powders in an agate mortar for only 5 min, the blended TiO₂/MOR samples showed higher photocatalytic reactivity as compared to the pure TiO₂ nano-particles. Since the high-silica zeolite powders are highly transparent in UV light regions, the incident UV light is effectively irradiated onto the whole part of the TiO₂ nano-particles without any loss of light intensity. Furthermore, the siliceous MOR zeolite powders effectively adsorb the gaseous acetaldehyde molecules and supply them onto the surfaces of the blended TiO₂ nano-particles, resulting in an enhancement of the photocatalytic reactivity.     

High activation of apatite-coated titanium dioxide using heat treatment

The purpose of this study was to improve the photocatalytic activity of TiO₂. A composite material in which apatite crystals were precipitated on the surface of TiO₂ was synthesized by immersing TiO₂ powder in pseudo-body solution. The composite material was heated in an attempt to improve the crystallization without inducing the anatase to rutile phase transformation of TiO₂ or reducing the specific surface area. In contrast to using TiO₂ alone, apatite-coated TiO₂ had a higher anatase-to-rutile transition temperature and lower specific surface area. In the methylene blue decolorization test, the decolorization rate of apatite-coated TiO₂ gradually increased with an increase in the heating temperature from 100 °C to 500 °C, and rapidly increased from 700 °C to 900 °C. The apatite-coated TiO₂ heated at 800 °C had the highest decolorization speed, which was approximately three times faster than that of apatite-coated TiO₂ without heating. It is assumed that the crystallinity of the anatase part is enhanced by heating, and the photocatalytic activity is improved.