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.     

The effects of different acids on the preparation of TiO2 nanostructure in liquid media at low temperature

Titania of different crystalline structures and morphology was prepared by the low temperature dissolution–reprecipitation process (LTDRP) of amorphous precursors in various acidic mediums at 70 °C for 8 h. The effects of different acids on the crystalline and morphology of titania nanostructures were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results showed that HCl, HNO₃ and their mixture favored the formation of rod-like rutile TiO₂, while H₂SO₄ and its mixture with HCl or HNO₃ retarded the formation of rutile but favored the formation of the anatase phase of with an irregular shape. The mechanism of the formation of various titania nanostructures was also discussed.     

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.     

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.     

Development of the fumed TiO2 having high content of rutile structure and dispesibility using the dry-type of surface modification and the thermal treatment

The effect of dry-type surface modification of a fumed TiO₂ and the thermal treatment were studied to synthesize the new fumed TiO₂ having a high content of rutile structure and high dispersibility. The fumed TiO₂ was modified with various metallic alkoxides to prepare precursors and next the resulted precursors were thermally-treated by the novel natural dropping method with a very short heating time, less than 1 s. The focus of this investigation was on the metallic alkoxide species as a surface modification agent and morphologies of both the precursor and thermally-treated fumed TiO₂. The morphologies and nanostructures of the obtained fumed TiO₂ were characterized. The carbon content and agglomerate of the precursor influenced on the transformation ratio from anatase to rutile structure. It was confirmed that the dry-type surface modification with tetraethoxysilane (TEOS) and titanium tetra-isopropoxide (TTIP) at room temperature is very effective method to prepare precursors for the next thermal treatment. The thermally-treated fumed TiO₂ modified with TTIP showed 100% rutile structure with pure TiO₂ composition at 1400 °C. The thermally-treated fumed TiO₂ modified with small quantities of TEOS exhibited both 100% rutile structure and excellent dispersibility. This high dispersibility caused from a sponge-like structural characteristic of the agglomerate and static electricity repellence by coated SiO₂ layer. The thermally-treated fumed TiO₂ modified with TEOS and TTIP showed the color tone shift can be attributed to rutile structure. It was revealed that the combination of dry-type surface modification and natural dropping thermal treatment is an attractive method to prepare the new fumed TiO₂ with 100% rutile structure maintaining the high dispersiblity.     

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.     

Ab initio study of phase stability in doped TiO2

Ab initio density functional theory calculations of the relative stability of the anatase and rutile polymorphs of TiO₂ were carried out using all-electron atomic orbitals methods with local density approximation. The rutile phase exhibited a moderate margin of stability of ~ 3 meV relative to the anatase phase in pristine material. From computational analysis of the formation energies of Si, Al, Fe and F dopants of various charge states across different Fermi level energies in anatase and in rutile, it was found that the cationic dopants are most stable in Ti substitutional lattice positions while formation energy is minimised for F^? doping in interstitial positions. All dopants were found to considerably stabilise anatase relative to the rutile phase, suggesting the anatase to rutile phase transformation is inhibited in such systems with the dopants ranked F?>?Si?>?Fe?>?Al in order of anatase stabilisation strength. Al and Fe dopants were found to act as shallow acceptors with charge compensation achieved through the formation of mobile carriers rather than the formation of anion vacancies.     

A facile template-free method for preparing bi-phase TiO2 nanowire arrays with high photocatalytic activity

Ordered bi-phase TiO₂ nanowire arrays were simply obtained by heat treating TiO₂ nanotube arrays prepared by a two-step anodization method. The nanowire arrays are composed of anatase and rutile phases with uniform diameters around 50 nm. The photocatalysis activities of TiO₂ nanowire arrays were characterized by quantifying the degradation of methyl orange solution. And the results indicated that the bi-phase nanowire arrays, especially obtained at 700 °C, showed much higher activity than that of P25 film or anatase TiO₂ nanotube array.     

The preparation of the anatase and rutile forms of Ag-TiO2 and hydrogen production from methanol/water decomposition

This study examined hydrogen production over Ag-TiO₂ photocatalysts containing Ag_xO, a conducting component. X-ray photon spectroscopy (XPS) confirmed that the Ag and Ag₂O components were dominant in the Ag-TiO₂ photocatalysts treated at 500 and 800 °C, respectively. The Ti2p bands in Ag-TiO₂ were shifted to lower binding energies, which were assigned to Ti³⁺, compared to pure TiO₂, and the shift was greater in the rutile structure than in the anatase. The measured full widths at half maximum (FWHM) of the Ag3d and Ti2p peaks were larger in the anatase structure than in the rutile structure in both TiO₂ and Ag-TiO₂. The H₂ production from methanol photodecomposition was greater over the rutile structure than over the anatase structure of TiO₂. Moreover, the amount of hydrogen was enhanced over Ag-TiO₂ compared to pure TiO₂; the production reached 17,124 μmol after 24 h over rutile Ag-TiO₂. After methanol photodecomposition, the amount of Ag component in the Ag-TiO₂ photocatalysts increased, while the Ag₂O component decreased.     

Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol-gel process

High density TiO₂ nanotube film with hexagonal shape and narrow size distribution was fabricated by templating ZnO nanorod array film and sol-gel process. Well-aligned ZnO nanorod array films obtained by aqueous solution method were used as template to synthesize ZnO/TiO₂ core-shell structure through sol-gel process. Subsequently, TiO₂ nanotube array films survived by removing the ZnO nanorod cores using wet-chemical etching. Polycrystalline anatase TiO₂ nanotube films were ∼ 1.5 μm long and ∼ 100 nm in inter diameter with a wall thickness of ∼ 10 nm.     

Reaction mechanism and kinetics analysis of the phase transformation of TiO2 from the anatase phase to the rutile phase

The kinetic mechanism of the phase transformation of TiO₂ from the anatase phase to the rutile phase was investigated. TiO₂ powders were prepared with different pH value of the starting solution via the thermal hydrolysis method in this study. The pH values of the starting solutions have significant effects on the phase transformation temperatures of the thermal hydrolysis reaction. As the reaction temperatures were raised, the conversion from the anatase phase to the rutile phase was increased. A core–shell morphology of the prepared TiO₂ samples was suggested via the signals of the anatase phase and the rutile phase in UV–vis spectrum analysis. Through the isothermal heating process of the reaction kinetics, the controlling reaction in the phase transformation process from the anatase phase to the rutile phase was determined to be the three-dimensional phase boundary controlled process. The activation energy of the phase transformation was increased with an increase in the pH value of the starting solution.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript> by tartarate gel method

A gel was formed when a mixture of TiOCl₂ and tartaric acid was heated on a water bath. Ultrafine powders of TiO₂ in the anatase phase were formed, when the gel was decomposed at 623 K and the mole ratio of tartaric acid to titanium was 2. The anatase phase was converted into rutile phase on annealing at higher temperatures, > 773 K. When initial ratio of titanium to tartaric acid was < 2, the decomposition of gel leads to the formation of mixed phases of rutile and anatase. However, pure rutile phase was not formed by the decomposition of gel for any ratio of tartaric acid and titanium. These powders were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and surface area measurements. The average particle size obtained for anatase phase was 3 nm whereas it was 30 nm for rutile phase. Raman scattering experiments were also performed to confirm both anatase and rutile phases.     

Photoelectrochemical properties of TiO2 nanotube arrays: effect of electrolyte pH and annealing temperature

The effect of electrolyte pH and annealing temperature on the formation of TiO₂ nanotube arrays in connection with the photoelectrochemical response was investigated in this article. Well-aligned TiO₂ nanotube arrays were fabricated by anodisation of Ti foil in an electrolyte consisting of 1?M of glycerol (85?wt% of glycerol and 15?wt% of water) with 0.5?wt% of NH₄F at 30?V for 30?min. The pH of the electrolyte was varied from pH 1 to 7. With the increase of electrolyte pH to neutral condition, the length of the nanotube arrays was increased from ～320 to 1100?nm. As-anodised TiO₂ nanotube arrays were amorphous in nature. However, anatase phase was observed after annealing at 400°C and polycrystalline anatase and rutile phase could be observed by heating up to 500°C in air atmosphere. Based on the results obtained, the length and crystalline phases of TiO₂ nanotube arrays affect the performance of photoelectrochemical response and photoconversion efficiency significantly.     

Structural resistance of chemically modified 1-D nanostructured titanates in inorganic acid environment

Sodium containing one-dimensional nanostructured layered titanates (1-D NSLT) were produced both from commercial anatase powder and Brazilian natural rutile mineral sands by alkali hydrothermal process. The 1-D NSLT were chemically modified with proton, cobalt or iron via ionic exchange and all products were additionally submitted to intensive inorganic acid aging (pH = 0.5) for 28 days. The morphology and crystal structure transformations of chemically modified 1-D NSLT were followed by transmission electron microscopy, powder X-ray diffraction, selected area electron diffraction and energy dispersive spectroscopy. It was found that the original sodium rich 1-D NSLT and cobalt substituted 1-D NSLT were completely converted to rutile nanoparticles, while the protonated form was transformed in a 70%–30% (by weight) anatase–rutile nanoparticles mixture, very similar to that of the well-known TiO₂-photocatalyst P25 (Degussa). The iron substituted 1-D NSLT presented better acid resistance as 13% of the original structure and morphology remained, the rest being converted in rutile. A significant amount of remaining 1-D NSLT was also observed after the acid treatment of the product obtained from rutile sand. The results showed that phase transformation of NSLT into titanium dioxide polymorph in inorganic acid conditions were controllable by varying the exchanged cations.Finally, the possibility to transform, through acid aging, 1-D NSLT obtained from Brazilian natural rutile sand into TiO₂-polymorphs was demonstrated for the first time to the best of authors' knowledge, opening path for producing TiO₂-nanoproducts with different morphologies through a simple process and from a low cost precursor.     

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.     

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.     

Synthesis of TiO2 thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO₂ thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, {TIP, Ti(OⁱPr)₄} and Bis(dimethylamido)titanium diisopropoxide, {BTDIP, (Me₂N)₂Ti(OⁱPr)₂} were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO₂ polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO₂ thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO₂ thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO₂ film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO₂ film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO₂ film synthesized with BTDIP precursor to apply dye-sensitized solar cell.     

Structure and luminescence properties of TiO2:Er3+ nanocrystals annealed at different temperatures

Erbium doped TiO₂ nanocrystals with the structures of anatase, pyrochlore Er₂Ti₂O₇, and rutile, characterized by X-ray diffraction, have been obtained at different annealing temperatures from 300 °C to 900 °C. The nanocrystalline size for anatase TiO₂ is reduced with increasing doped erbium concentration. Following ultraviolet 325 nm irradiation, the intensity of the green emission is the most intense for the TiO₂:Er³⁺ nanocrystals with a structure of pyrochlore Er₂Ti₂O₇, which evolves from the structure of anatase annealed at 800 °C. Moreover, following ultraviolet 325 nm and infrared 980 nm irradiation, the visible emission spectra for the nanocrystals annealed at 900 °C change drastically. Correspondingly, the structure of anatase disappears, while that of rutile becomes dominant, which indicates that phase transformation occurs.     

Preparation and characterization of nitrogen-doped titania nanotubes

Nitrogen-doped TiO₂ nanotubes were synthesized by annealing of the anodized titania nanotubes with ammonia at the temperature of 500 °C. The ordered structure of titania nanotubes maintained after the nitrogen doping process, as is evidenced by SEM observations. Detailed structural analysis revealed that the phase transformation temperature of titania nanotube from anatase to rutile is decreased after nitrogen doping. The XRD patterns of nitrogen-doped titania exhibit an increased peak intensity and a decreased FWHM in the (110) peak of rutile in comparison with those of undoped titania under the same annealing conditions, indicating that nitrogen doping may have facilitated the phase transition at the annealing temperature of 500 °C, which is in consistence with the analysis of Raman spectra as the comparison of A_1g and E_g Raman peaks of rutile in the nitrogen-doped and undoped titania.