Effect of Nb and Sc doping on the phase transformation of sol-gel processed TiO2 nanoparticles

Nb and Sc doped TiO2 nanoparticles were synthesized via sol-gel technique. Dopant concentration of each element was varied from 0.5 to 1.5 atomic%. The effect of metal ion doping and calcination temperatures on anatase to rutile phase transformation has been investigated. Samples were analyzed by various analytical methods such as X-ray diffraction (XRD), Transmission Electron Microscope (TEM), X-ray Photoelectron Spectroscopy (XPS) and Energy Dispersive X-ray Spectroscopy (EDS). XRD analyses showed that Nb and Sc doped samples calcined at 300 degrees C and 350 degrees C, respectively, were crystalline and had an anatase structure. Results showed that anatase was stable up to 700 degrees C annealing temperature for samples doped with 0.5 atomic% Nb. There was a sharp transition from anatase to rutile phase above 700 degrees C and complete rutile structure was obtained at 750 degrees C. However, the transformation from anatase to rutile was not so sharp in samples doped with 1.0 atomic% and 1.5 atomic% Nb. Results indicated that higher concentration of Nb helps to stabilize the anatase phase. For samples doped with 0.5 atomic% Sc, anatase phase is stable up to 650 degrees C. Transformation from anatase to rutile starts at temperature above 650 degrees C and 100% rutile phase was obtained at 800 degrees C while for samples doped with 1.0 atomic% and 1.5 atomic% Sc, the complete transformation from anatase to rutile takes place at an even higher temperature. Results indicate that increasing the calcination time from 0.5 to 2.0 hours at 500 degrees C does not affect the stability of anatase phase. However, TEM and XRD data showed that the increase in the annealing time leads to an increase in particles size. The rutile to anatase concentration ratio increased with temperature above the phase transformation temperature. The activation energy for the phase transformation from anatase to rutile for doped and undoped samples was also measured. There was a general rise in the activation energy with increasing dopant concentration.     

Preparation of immobilized nano-columnar TiO2 grains by chemical vapor deposition

Nano-columnar TiO2 grains are prepared and immobilized by chemical vapor deposition using TiCl4, H2 and O2 at low temperature. The structure of TiO2 is analyzed by X-ray diffraction (XRD), the morphology is observed by scanning electron microscopy (SEM) and the adhesion is estimated by measuring the critical load in scratch test. Results show that the structure of TiO2 films depend on the deposition temperature changing from amorphous, anatase, rutile, and both anatase and rutile phases as prepared at temperatures of 200, 300, 400 and 500 degrees C, respectively. The nano-columnar TiO2 grains are formed in both rutile and anatase phases, while it could be only rutile phase by increasing TiCl4 flow rate. The morphologies of TiO2 changes from smooth to nano-columnar grains as the deposition temperature increased from 200 to 400 degrees C. Excellent adhesion strength of crystalline TiO2 was obtained and it could be improved by increasing the TiCl4 flow rate in range of 0.3-0.6 sccm, where the critical load of TiO2 increases from 17 to 21 N.     

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.     

Preparation of rutile and anatase phases titanium oxide film by RF sputtering

Titanium oxide films were prepared by RF magnetron sputtering onto glass substrates. The effects of RF power and deposition temperature on crystalline structure, morphology and energy gap were investigated, which were analyzed by X-ray diffraction, SEM and UV-Vis spectrometer, respectively. Results show that rutile phase is the favored structure during deposition. Applying RF power in the range of 50-250 W, the amorphous, rutile, and both rutile and anatase phases TiO2 films were obtained in sequence, while the content of anatase is similar in the range of 34-37% although the RF power increases. Increasing the deposition temperature, the anatase phase coexists in the rutile phase in the range of 100-200 degrees C, and the content of anatase increases from 20 to 41% with the deposition temperature. In addition, according to the morphology observation, the granulous surface is found in rutile phase while facetted surface in anatase phase when titanium oxide films deposited at various RF powers and substrate temperatures. The band gap energy of titanium oxide evaluated from (alphahv)1/2 versus energy plots show that the energy gap decreases with RF power increasing.     

Synthesis of Mixed-Phase TiO2 Powders in Salt Matrix and Their Photocatalytic Activity

Three mixed-phase TiO₂ powders, containing ～80 volume % anatase and ～20 volume % rutile, were prepared from amorphous titanium hydroxide and three different salt matrices—pure sodium chloride, pure Na₂CO₃, and pure disodium hydrogen phosphate (DSP). Amorphous titanium hydroxide and salt mixtures were heat treated at 875°C in a rapid thermal annealing system for different times, according to the time–temperature phase transformation graphs. Time-dependent UV degradation of aqueous solutions of methylene blue dye (15 ppm) in the presence of mixed-phase powders was used to monitor the activity of the catalysts. Microstructural study of the powders by scanning electron microscope and transmission electron microscope combined with phase analysis by XRD and optical absorbance by UV-absorption spectroscopy indicated that the higher photocatalytic activity of the powder obtained from pure DSP salt could be explained by its smaller rutile particle size and anatase–rutile interparticle bonding.     

Effect of heat treatment on phase transition of nanotubular titanium oxide arrays

The purpose of this study was to investigate the effects of heat treatment on the cystallinity of titanium nanotubes. The titanium nanotubes had diameters ranging from 90-95 nm, lengths between 400-500 nm, and thicknesses of 11 nm. After heat treatment at high temperatures, the diameter and length of the nanotubes decreased, whereas the thickness increased. The titanium nanotubes exhibited amorphous + anatase phases at 300 degrees C, anatase + rutile phases at 500 degrees C and a rutile phase at 800 degrees C.     

Structural Characteristics of TiO2 Ceramic Coating by Micro-Plasma Oxidation

TiO2 ceramic coatings with thickness of 20 μm were formed on the surface of pure titanium by micro-plasma oxidation. Their micro-structures were investigated by by using X-ray diffraction and their surface images were detected by using scan electronic microscope. There were three kinds of TiO2 coatings, pure anatase type TiO2 phase, mixed phases consisted of rutile type TiO2 phase and anatase type TiO2 phase, pure rutile type TiO2 phase. The coating surface with the pure anatase type TiO2 phase is rough, while the coating surface with the pure rutile type TiO2phase is smooth. The upper coating surface with the mixed type TiO2 phases is anatase type TiO2 structure and the subsurface of the TiO2 coating is rutile type TiO2structure.     

Effect of silver additions on the structural properties and phase composition of TiO<Subscript>2</Subscript>/Ag composites

We have studied the effect of silver nitrate additions on the anatase–rutile transformation of titanium dioxide in TiO₂/Ag composites at low temperature (500°C). The structure and phase composition of the composites with different Ag(I) concentrations have been determined by X-ray diffraction and transmission electron microscopy. The results demonstrate that the percentage of rutile increases with increasing Ag(I) ion concentration, reaching 60 wt %. A mechanism of the anatase–rutile transformation in the composites has been proposed.     

Effect of high-temperature heat treatment duration on the purity and microstructure of MWCNTs

The effect of high-temperature heat treatment on purity and structural changes of multiwalled carbon nanotubes (MWCNTs) were studied by subjecting the raw MWCNTs (pristine MWCNTs) to 2600^°C for 60 and 120 min. Thermogravimetric analysis (TGA), X-ray diffraction, Raman spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to study the effect of heat-treatment duration on the purity and structural changes of MWCNTs. Results show that high-temperature heat treatment can be used to purify MWCNTs with proper optimization of treatment time. It was observed that 60 min heat treatment of raw MWCNTs imparts high purity and structural perfection to MWCNTs, while 120 min heat treatment imparts structural degradation to MWCNTs with collapse of the innermost shells. The present study indicates that metal impurities act as moderators in controlling the degradation of MWCNTs up to certain duration, and once the metal impurities escape completely, further heat treatment degrades the structure of MWCNTs.     

Anatase and rutile TiO2 thin films prepared by reactive DC sputtering at high deposition rates on glass and flexible polyimide substrates

Titanium oxide thin films have been prepared by reactive DC sputtering at room temperature on soda-lime glass (SLG) and flexible polyimide (Kapton) substrates. The sputtering conditions have been adjusted in order to achieve high deposition rates between 15 and 45 nm/min. Post-deposition heating of the samples has been performed at 350 °C in nitrogen during 30 min. The crystalline structure of these films and their optical, morphological, and electric characteristics have been studied before and after annealing by X-ray diffraction, spectrophotometric measurements, atomic force microscopy, and the four-point probe method. The optical data indicate that pure anatase phase, which crystallizes after the heating process, is obtained on both SLG and Kapton substrates at the lowest deposition rate (15 nm/min). In this case, the samples exhibit high electric resistivity above 300 Ωcm. Otherwise, for the highest deposition rate (45 nm/min), crystalline rutile is identified in the as-grown and heated films, with a lower optical gap energy than anatase and also a lower resistivity that reaches 0.3 Ωcm after heating. At intermediate deposition rates, anatase and rutile coexist in the samples as has been verified by X-ray diffraction, although the overall optical and electric characteristics are dominated by the rutile phase. Analogous titanium oxide layers have been obtained on SLG and Kapton, and this opens the possibility of substituting flexible plastics for conventional glass substrates.     

Preparation and photocatalytic properties of mixed-phase titania nanospheres by laser ablation

Laser ablation technique was adopted to prepare titania nanospheres; scanning electron microscope (SEM), X-ray diffraction (XRD) and transmission electron microscope (TEM) were employed to characterize the morphology and structure of the product. The results demonstrate that TiO₂ nanospheres with mixed-phase (rutile and anatase) structure were successfully fabricated by laser ablation of titanium target in water. We proposed that changed temperature and pressure after the laser ablation is responsible for the co-existence of the rutile phase and the anatase phase. The mixed-phase titania nanospheres (MTNSs) show superior photocatalytic properties compared with commercial titania powder, which is ascribed to the mixed-phase structure.     

Effect of cobalt doping on the phase transformation of TiO2 nanoparticles

Co-doped TiO2 nanoparticles containing 0.0085, 0.017, 0.0255, 0.034, and 0.085 mol % Co(III) ion dopant were synthesized via sol-gel and dip-coating techniques. The effects of metal ion doping on the transformation of anatase to the rutile phase have been investigated. Several analytical tools, such as X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray analysis (EDAX) were used to investigate the nanoparticle structure, size distribution, and composition. Results obtained revealed that the rutile to anatase concentration ratio increases with increase of the cobalt dopant concentration and annealing temperature. The typical composition of Co-doped TiO2 was Ti(1-x)Co(x)O2, where x values ranged from 0.0085 to 0.085. The activation energy for the phase transformation from anatase to rutile was measured to be 229, 222, 211, and 195 kJ/mole for 0.0085, 0.017, 0.0255, and 0.034 mol % Co in TiO2, respectively.     

Microwave-hydrothermal process for the synthesis of rutile

The synthesis of pure rutile titanium dioxide is not an easy achievement, as the crystallization process generally leads to mixtures of two or even three phases; moreover the synthetic processes normally used by industry require harsh reaction conditions. We carried out the synthesis of titanium dioxide from an aqueous titanium tetrachloride solution under microwave irradiation in the reaction time range of 5-120 min. We mostly obtained mixtures of rutile and anatase, but obtained single-phase rutile after a 2-h treatment at 160 °C; transmission electron micrographs revealed well-dispersed spherical nanoparticles. We also investigated the effects of dilution and addition of a dispersant (polyvinylpyrrolidone) on phase crystallization and particle shape.     

Characterization of TiO2 nanoparticles prepared using different surfactants by sol–gel method

Titania nanoparticles have been prepared using different surfactants such as, acetic acid (AA), oleic acid (OA), oley amine (OM), and a mixture of OA + OM at room temperature by sol–gel method. TiO₂ nanoparticles were collected by centrifugation of the precipitate obtained during gel formation. The collected samples were annealed at 550 and 950 °C to study the effect of annealing temperature on the structural and optical properties. The crystal structure and optical properties of titania nanoparticle is investigated by means of X-ray diffraction, Raman spectroscopy, UV–visible spectroscopy, and photoluminescence. After heat treatment at 950 °C, the mixed rutile and anatase phase of TiO₂ was revealed for the sample prepared with AA, whereas pure rutile phase was observed for the sample prepared in presence of OA, OM and the mixture of OA + OM. The energy band gap and transmittance of measured for titania nanoparticles was found to be systematically reduced with increase in annealing temperature for each surfactant. The ideality factor decreases with increase in annealing temperature for all surfactants could be related to the voltage dependence of the standard deviation of the distribution of barrier heights.     

Synthesis of Single-Crystal TiO2 Nanowire Using Titanium Monoxide Powder by Thermal Evaporation

TiO 2 nanowires were synthesized successfully in a large quantity by thermal evaporation using titanium monoxide powder as precursor. X-ray diffraction results showed that all the products were pure rutile phase of TiO 2 . According to microstructural observations, the nanowires have two typical morphologies, a long straight type and a short tortuous type. The straight nanowires were obtained at a wide temperature range of 900-1050 ℃, while the tortuous ones were formed below 900 ℃. Transmission electron microscopy characterization revealed that both the straight and the tortuous nanowires are single-crystal rutile TiO 2 . The preferential growth direction of the nanowires was determined as [110] orientation according to electron diffraction and high-resolution image analyses. The morphological change of TiO 2 nanowires was discussed by considering the different atomic diffusion rates of Ti atoms caused by the phase transformation in Ti substrate at around 900 ℃.     

The crystalline phase stability of titania particles prepared at room temperature by the sol-gel method

Titania particles having anatase, brookite and rutile phase were prepared at various H⁺/TTIP (Titaniumtetraisopropoxide) mole ratios and room temperature by the sol-gel method. The crystalline phases according to the variation of the post heat treatment temperature were observed. The crystalline phase and the phase transformation, morphology, and crystallite size were identified by using XRD, TG/DTA, Raman spectroscopy and TEM. The brookite phase of titania particles prepared at the H⁺/TTIP mole ratio of 0.02 and room temperature was not transformed into anatase or rutile even with the heat treatment at 750°C, and also the anatase phase was stable at the temperature as high as 850°C. However, the titania particles prepared at the H⁺/TTIP mole ratio of 0.67, which contained the mixed phases of anatase, brookite, and rutile at room temperature, showed only rutile phase at temperature of 750°C. It was thus shown that the initial crystalline phase of the primary particles prepared at room temperature had an important effect on the phase transformation behavior upon post heating. Phase transformation from brookite to anatase and subsequently to rutile occurred with heating.     

Synthesis and photocatalytic activity of stable nanocrystalline TiO(2) with high crystallinity and large surface area

Superior photoactive TiO(2) nanopowders with high crystallinity and large surface area were synthesized by a hydrothermal process in the presence of cetyltrimethylammonium bromide and a post-treatment with ammonia. The prepared photocatalysts were characterized by X-ray diffraction (XRD), Raman spectroscopy, N(2) adsorption-desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectra (DRS) and surface photovoltage spectroscopy (SPS). The prepared nanocrystallites were highly resistant to thermal sintering, and the calcinations up to 900 degrees C were shown to enhance the crystallinity of the anatase phase without any rutile phase and the separation rate of photoinduced charges of TiO(2) particles. It remained as large as 196 and 125 m(2)/g even after calcinations at 700 and 800 degrees C, respectively. The photocatalytic activity of prepared photocatalysts was obviously higher than that of commercial Degussa P25 on the photodegradation of methylene blue and phenol in water under ultraviolet-light irradiation, and the sample calcined at 800 degrees C afforded the highest photocatalytic activity.     

Mechanical treatment of TiO2 and ZrO2 oxide mixtures

The mixed ZrO2-TiO2 system (5-50 wt% of ZrO2) has been studied to investigate the influence of the mechanical treatment on its physicochemical properties depending on the composition, time of milling (5, 10 and 20 min, r.p.m. 82) and temperature (400, 550 and 700 degrees C). Samples were characterized by Raman spectroscopy, X-ray powder diffraction, Scanning Electron Microscopy coupled with Energy Dispersion X-ray analyzer, High Resolution-Transmission Electron Microscopy and nitrogen adsorption porosimetry. Results show that srilankite (TiZrO4) phase has been produced. No influence of the milling time and temperature on the phase composition is observed. The presence of zirconia increases the thermal stability of anatase phase up to 700 degrees C hindering the anatase rutile phase transformation.     

One-dimensional TiO2 nanomaterials: preparation and catalytic applications

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.