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.     

Effect of calcination temperature on the textural properties and photocatalytic activities of highly ordered cubic mesoporous WO3/TiO2 films

Highly organized cubic mesoporous WO3/TiO2 films were successfully prepared by evaporation-induced self-assembly (EISA) process, employing triblock copolymer as template. The characterization results by XRD, SEM, TEM, UV-Vis. spectrophotometry, and nitrogen adsorption-desorption isotherms reveal that the mesoporous films are made up of well-defined 3-D cubic (lm3m space group) mesoporous structure and nanocrystalline anatase frameworks with high surface area, uniform pore sizes and excellent optical transparency. Photocatalytic properties of the mesoporous WO3/TiO2 films in decomposing gaseous 2-propanol to CO2 were analyzed as a function of calcinations temperature. The highest photocatalytic activity was obtained for the films calcined at 450 degrees C, which possess an appropriate crystallinity and relevant ordering of mesoporous structure. It was found that that long-range ordering of mesopores is one of the important factors in determining the photocatalytic degradation of gaseous organics.     

Low temperature synthesis and visible light driven photocatalytic activity of highly crystalline mesoporous TiO2 particles

Mesoporous TiO2 powder materials with a high crystallinity have been prepared by evaporation induced self assembly (EISA) process using titanium tetraisopropoxide (TTIP) and pluronic P123 surfactant (EO20PO70EO20) as titanium source and structure-directing reagent, respectively. The prepared materials were characterized by low and wide-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), optical absorption, and N2 adsorption-desorption experiments. The crystallinity of the materials was controlled by varying the calcination temperature. The resulting TiO2 materials showed highly crystalline structure with uniform particle size which increases from 11.8 to 23.8 nm with increasing the calcination temperature from 400 to 600 degrees C, respectively, whereas the specific surface area decreases from 125 to 40 m2/g. TEM and XRD results revealed that the calcination temperature of 600 degrees C is the best condition to obtain highly crystalline mesoporous TiO2. The photocatalytic activity of the TiO2 mesoporous materials with different crystallinity and textural parameters has been studied in the decomposition of methylene blue (MB) dye molecules under visible light irradiation. Among the mesoporous TiO2 materials studied, the material with the highest crystallinity, prepared at 600 degrees C, showed the best photocatalytic performance in the decomposition of MB under visible light in a short time.     

Synthesis of photocatalytic TiO2 thin films via the high-pressure crystallization process at low temperatures

TiO2 thin films with a monophasic anatase structure were synthesized via a high-pressure crystallization (HPC) process which successfully lowered the crystallization temperature of TiO2 films from 350 to 150 degrees C. The thermal budget and energy consumption during the crystallization process were markedly reduced and dense films without cracks were obtained. During the HPC process, crystallization took place throughout the films and TiO2 films with uniform crystallinity were obtained. The HPC process also led to an enhancement in the wettability of TiO2 thin films. The hydrophilicity of the films increased with heating temperatures via high-pressure annealing. In comparison with the conventional annealing, the HPC process not only produced TiO2 films with superior photo-induced super-hydrophilicity, but also led to higher photocatalytic activity of the films. The HPC process was confirmed to provide a new route for synthesizing well-crystallized anatase TiO2 thin films with high photocatalytic activity and good wettability at low temperatures.     

Effects of calcination temperature on the morphology, structure and photocatalytic activity of titanate nanotube thin films

"Titanate nanotube thin films were synthesized on titanium substrate via a simple hydrothermal method. The as-prepared film was composed of Na₂Ti₃O₇, and then transformed into H₂Ti₄O₉·H₂O after acid washing process. However, H₂Ti₄O₉·H₂O was thermally unstable. The effect of calcination temperature on its morphology (nanotube, nanosheet, nanorod or a lotus-root-like appearance), structure and photocatalytic activity was carried out by annealing the films at 300-900 °C in the static air and then analyzing by X-ray diffraction, scanning electron microscope and transmission electron microscope. Based on the results, the possible evolution mechanisms were discussed for no-acid (washed with distilled water) and acid washed (washed with dilute HNO₃) samples, respectively. Finally, the photocatalytic activity of acid washed films calcined at different temperatures was evaluated by photodegradation of methyl orange (MO) under ultraviolet light. The results indicated that the film obtained at 500 °C showed the highest rate for decomposing MO solution, which could be explained by its unique surface morphology and crystal structure.     

Photocatalytic oxidation of nitric oxide with immobilized titanium dioxide films synthesized by hydrothermal method

Gas-phase photocatalytic oxidation (PCO) of nitric oxide (NO) with immobilized TiO2 films was studied in this paper. The immobilized TiO2 films were synthesized by hydrothermal method. The characterization for the physicochemical properties of catalysts prepared under different hydrothermal conditions were carried out by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller measurements (BET) and scanning electron micrograph (SEM). It was found that the PCO efficiency of the catalyst was mainly depended on the hydrothermal conditions. The optimal values of hydrothermal temperature and hydrothermal time were 200 degrees C and 24 h, respectively. Furthermore, it was also known that the photocatalytic efficiency would decrease remarkably when the calcination temperature was over than 450 degrees C. Under the optimal conditions (hydrothermal condition: 200 degrees C for 24 h; calcination temperature: 450 degrees C), the photocatalytic efficiency of catalyst could reach 60% higher than that of Degussa P25.     

Nitrogen-doped TiO2 nanotube array films with enhanced photocatalytic activity under various light sources

Highly ordered nitrogen-doped titanium dioxide (N-doped TiO(2)) nanotube array films with enhanced photocatalytic activity were fabricated by electrochemical anodization, followed by a wet immersion and annealing post-treatment. The morphology, structure and composition of the N-doped TiO(2) nanotube array films were investigated by FESEM, XPS, UV-vis and XRD. The effect of annealing temperature on the morphology, structures, photoelectrochemical property and photo-absorption of the N-doped TiO(2) nanotube array films was investigated. Liquid chromatography and mass spectrometry were applied to the analysis of the intermediates coming from the photocatalytic degradation of MO. The experimental results showed that there were four primary intermediates existing in the photocatalytic reaction. Compared with the pure TiO(2) nanotube array film, the N-doped TiO(2) nanotubes exhibited higher photocatalytic activity in degradating methyl orange into non-toxic inorganic products under both UV and simulated sunlight irradiation.     

Ce3+掺杂钛酸钡纳米管薄膜的制备与性能

以阳极氧化制备的TiO_2纳米管薄膜为模版,通过水热法制备了Ba_(1-x)Ce_xTiO_3(0≤x≤0.08)纳米管薄膜,研究了Ba_(1-x)Ce_xTiO_3的结构、表面形貌及其电性能。采用X射线衍射仪表征其晶体结构,采用扫描电子显微镜和透射电子显微镜观察其表面及断口形貌,采用宽频介电阻抗谱仪测试其介电性能。结果表明,在较为温和的条件下用水热法成功制备出立方相结构的Ba_(1-x)Ce_xTiO_3纳米管薄膜,纳米管孔径在80~95nm之间;将制备的Ba_(1-x)Ce_xTiO_3经退火后生成多晶的Ba1-xCexTiO3纳米管薄膜,且样品的管外径尺寸在90~100nm之间,管壁的厚度为25~30nm,介电常数在1kHz下最高可达472,介电损耗为0.41。     

Fast fabrication of long TiO2 nanotube array with high photoelectrochemical property on flexible stainless steel

Oriented highly ordered long TiO2 nanotube array films with nanopore structure and high photoelectrochemical property were fabricated on flexible stainless steel substrate (50 microm) by anodization treatment of titanium thin films in a short time. The samples were characterized by means of field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and photoelectrochemical methods, respectively. The results showed that Ti films deposited at the condition of 0.7 Pa Ar pressure and 96 W sputtering power at room temperature was uniform and dense with good homogeneity and high crystallinity. The voltage and the anodization time both played significant roles in the formation of TiO2 nanopore-nanotube array film. The optimal voltage was 60 V and the anodization time is less than 30 min by anodizing Ti films in ethylene glycerol containing 0.5% (w) NH4F and 3% (w) H2O. The growth rate of TiO2 nanotube array was as high as 340 nm/min. Moreover, the photocurrent-potential curves, photocurrent response curves and electrochemical impedance spectra results indicated that the TiO2 nanotube array film with the nanoporous structure exhibited a better photo-response ability and photoelectrochemical performance than the ordinary TiO2 nanotube array film. The reason is that the nanoporous structure on the surface of the nanotube array can separate the photo electron-hole pairs more efficiently and completely than the tubular structure.     

Photocatalytic properties of titanate nanotube powders prepared by alkaline hydrothermal method

This paper reports the photocatalytic activities of titanate nanotubes (TNTs) synthesized using different methods and compares them with that of P25. Rhodamine B was selected as the organic compound to be decomposed by the microwave/UV/photocatalyst hybrid process. The as-prepared TNT had titanate crystalline structure, whereas the TNT calcined at 723 K was phase-transformed into anatase structure. When the as-prepared TNT was ion-exchanged using HCl, Na+ content was reduced from 8.36 wt% to 0.03 wt%. The ion-exchanged TNT showed the highest photocatalytic activity among the TNTs tested in this study, but it was lower than that of P25.     

Effects of calcination temperatures on photocatalytic activity of SnO2/TiO2 composite films prepared by an EPD method

SnO2/TiO2 composite films were fabricated on transparent electro-conductive glass substrates (F-doped SnO2-coated glass:FTO glass) via an electrophoretic deposition (EPD) method using Degussa P25 as raw materials, and were further characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FESEM), UV-vis diffuse reflectance spectra and Photoluminescence spectra (PL). XRD and XPS results confirmed that the films were composed of TiO2 and SnO2. FESEM images indicated that the as-prepared TiO2 films had roughness surfaces, which consisted of nano-sized particles. The effects of calcination temperatures on the surface morphology, microstructures and photocatalytic activity of SnO2/TiO2 composite films were further investigated. All the prepared SnO2/TiO2 composite films exhibited high photocatalytic activities for photocatalytic decolorization of Rhodamine-B aqueous solution. At 400 degrees C, the SnO2/TiO2 composite films showed the highest photocatalytic activity due to synergetic effects of low sodium content, good crystallization, appropriate phase composition and slower recombination rate of photogenerated charge carriers.     

Improved catalytic capability of mesoporous TiO2 microspheres and photodecomposition of toluene

A series of mesoporous titanium dioxide microspheres were calcined at various temperatures to improve their photocatalytic activity. The prepared catalysts were characterized by XRD, SEM, TEM, TG-DTA, UV-vis, and N(2) adsorption-desorption measurements, and their photocatalytic performances were investigated by photooxidation of gaseous toluene. As the results revealed, calcination temperatures obviously influenced the surface morphology and photocatalytic activity of the mesoporous TiO(2) microspheres. The noncalcined samples had a mesoporous structure of the anatase phase. The sample calcined at 400 °C showed a superior photocatalytic performance, which had a reaction rate constant 2-fold higher than that of P(25). The enhanced photoreactivity is possibly due to the synergetic effects of the mesoporous structure and light-transmittance ability of the catalysts. Two new reaction intermediates were discovered as well, and a tentative degradation pathway was proposed.     

Crystal structure and photocatalytic properties of titanate nanotubes prepared by chemical processing and subsequent annealing

Anatase TiO₂ nanoparticles were synthesized from sol–gel processing, and they were used as a precursor for titanate nanotubes (TNT) formation. TNT were synthesized under reflux heating of anatase TiO₂ in concentrated NaOH solution followed by repeated washing with distilled water and 0.1 M HCl. The nanotubular structure was preserved till 450 °C, above which nanorod formation started. The as-synthesized nanotubes were found to have mixed crystal structure of anatase and Na _x H_2?x Ti₃O₇·nH₂O (where 0 < x <  2), contrary to what has been reported before. The XRD peaks of titanate were slightly shifted to higher angles upon calcination along with prominent anatase peaks. Complete transformation to nanorods occurred at 600 °C and crystal structure was transformed to Na₂Ti₆O₁₃ and anatase. Sodium presence in TNT was confirmed by EDX, and Na–O and H–O–H along with Ti–OH vibrations were found by FTIR. Ti–OH/H–O–H vibrations were less prominent for samples calcined at 500 °C and above, which confirms structural water loss is associated with morphological change. The as-synthesized TNTs had a specific surface area of 157 m² g^?1, and it decreased by increasing calcination temperature. TNTs were applied to methylene blue aqueous solution to observe their decolorization capability under UV irradiation. The as-synthesized TNTs showed enhanced photocatalytic decolorization as compared to anatase titania nanoparticles due to presence of Ti–OH groups and higher specific surface area. The photocatalytic activity reduced when TNTs were annealed at high temperatures. The changes in the photocatalytic activity are related to the existence of hydroxyl groups in the structure, decrease in specific surface area of annealed nanotubes, change in morphology from nanotubes to nanorods, and bandgap shift to visible light when TNTs were calcined at higher temperatures.     

Photoactivity of anatase–rutile TiO2 nanotubes formed by anodization method

Titania (TiO₂) nanotubes were prepared by anodizing titanium (Ti) foils in an electrochemical bath consisting of 1 M glycerol with 0.5 wt.% NH₄F.The pH of the bath was kept constant at 6 and the anodization voltage was varied from 5 V, 20 V to 30 V. It is found that the morphology of the anodized titanium is a function of anodization voltage with pits-like oxide formed for the sample made at 5 V and samples made at 20 V and 30 V consisted of well-aligned nanotubes growing perpendicularly on the titanium foil. However, the nanotubes formed on the samples made at 30 V were not uniform in terms of the nanotubes' diameter and wall thickness. Regardless of the anodization voltage, as anodised samples were amorphous. The crystal structure evolution was studied as a function of annealing temperatures and was characterised by X-ray diffraction and Raman spectroscopy analyses. Crystallization of the nanotubes to anatase phase occurred at 400 °C while rutile formation occurred at 700 °C. Disintegration of the nanotube arrays was observed at 600 °C and the structure completely vanished at 700 °C. TiO₂ nanotube annealed at 400 °C and containing 100% anatase revealed the highest photocatalytic activity for the degradation of methyl orange. Consequently, these results indicate that diameter, wall thickness, crystal structure and degree of crystallinity of the TiO₂ nanotube arrays are the important factors influencing the efficiency of the photocatalytic activity.     

Influence of structure parameters and crystalline phase on the photocatalytic activity of TiO2 nanotube arrays

Titanium oxide nanotube arrays (TiO2-NTAs) with different diameters and lengths are prepared by anodization of titanium foils in a water/ethylene glycol solution (5:95 V/V) containing 0.3 wt% NH4F. The effects of the diameters, lengths and crystalline phases of the NTAs on the photocatalytic (PC) activity are systematically evaluated. Larger pore diameter results in higher PC activity. The PC activity increases initially and then decreases with lengths for TiO2-NTAs and the optimal length that yields the highest PC activity is observed to be 6.2 microm. The crystalline phase and corresponding PC activity depend on the calcination temperature and their relationship is also investigated. The amorphous-to-anatase and anatase-to-rutile phase transitions initially occur at 300 and 500 degrees C, respectively. The PC activity of TiO2-NTAs initially increases with calcination temperature from 250 to 500 degrees C and then decreases at higher calcination temperature. The enhanced PC activity observed from the samples annealed at 250-450 degrees C is attributed to the better anatase crystalline structure at higher calcination temperature. The highest PC activity with regard to photodecomposition of methyl orange is observed from TiO2-NTAs calcined at 500 degrees C, which coincides with the anatse-to-rutile phase transformation. The synergistic effect of the anatase TiO2-NTAs and rutile barrier layers facilitate interfacial electron transfer consequently enhancing the PC activity. Further elevation of the calcination temperatures to 550 and 600 degrees C exhibits diminished PC activity because the NTs become shorter due to conversion of the bottom of anatase NTs into rutile film.     

Structural transformation, photocatalytic, and field-emission properties of ridged TiO2 nanotubes

Self-organized, freestanding TiO(2) nanotube arrays with ridged structures have been fabricated using a one-step anodic oxidation method. Their structural, photocatalytic, and field-emission (FE) properties have systematically been investigated. The as-synthesized nanostructures have been characterized using XRD, Raman spectroscopy, SEM, and HRTEM. The experimental results show that after an annealing process, the starting amorphous nanotubes have been turned into anatase phase structures, and the tube walls have been decorated with nanoparticles, different from the original ridged nanotubes. Furthermore, the anatase phase nanotubes have demonstrated better photocatalytic properties than their amorphous counterparts, which is caused by the larger surface area and improved crystallinity. With respect to FE properties, the as-grown nanotubes have the lower turn-on field E(to) and the higher field enhancement factor β compared to the annealed nanotubes. The relationship between E(to), β, and the tube arrangements and morphologies has also been discussed.     

Effects of Fe-doping on the photocatalytic activity of mesoporous TiO2 powders prepared by an ultrasonic method

Highly photoactive nanocrystalline mesoporous Fe-doped TiO(2) powders were prepared by the ultrasonic-induced hydrolysis reaction of tetrabutyl titanate (Ti(OC(4)H(9))(4)) in a ferric nitrate aqueous solution (pH 5) without using any templates or surfactants. The as-prepared samples were characterized by thermogravimetry and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), N(2) adsorption-desorption measurements, UV-visible adsorbance spectra (UV-vis) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities were evaluated by the photocatalytic oxidation of acetone in air. The results showed that all the Fe-doped TiO(2) samples prepared by ultrasonic methods were mesoporous nanocrystalline. A small amount of Fe(3+) ions in TiO(2) powders could obviously enhance their photocatalytic activity. The photocatalytic activity of Fe-doped TiO(2) powders prepared by this method and calcined at 400 degrees C exceeded that of Degussa P25 (P25) by a factor of more than two times at an optimal atomic ratio of Fe to Ti of 0.25. The high activities of the Fe-doped TiO(2) powders could be attributed to the results of the synergetic effects of Fe-doping, large BET specific surface area and small crystallite size.     

Preparation and photocatalytic activity of N-doped TiO2 nanotube array films

The N-doped TiO₂ nanotube array films were fabricated directly by one-step electrochemical anodic oxidation of Ti foils in an HF electrolyte containing ammonium and nitrate ions. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDX), and ultraviolet–visible (UV–vis) absorption spectroscopy, respectively. The photocatalytic activities were evaluated by the degradation of methyl orange (MO) under visible light irradiation. The results showed that N dopant was successfully introduced into the TiO₂ nanotube array films. The N-doped TiO₂ nanotube array films showed a red shift and an enhancement of the absorption in the visible light region compared to the undoped sample. The photocatalytic activities of the N-doped TiO₂ samples were much higher than those of the undoped sample. A maximum enhancement of photocatalytic activity was achieved for the N-doped TiO₂ sample prepared in 0.07 M HF electrolyte containing 1.0 M NH₄NO₃, and 81% of MO was degraded in 150 min under visible light irradiation.     

Hydrothermal synthesis of hemisphere-like F-doped anatase TiO<Subscript>2</Subscript> with visible light photocatalytic activity

Hemisphere-like F-doped anatase TiO₂ has been synthesized by hydrothermal treatment of TiF₄ aqueous solution in the presence of starch at 130 °C for 10 h, and then calcined at 450 °C for 2.5 h in air. The as-synthesized product has been investigated by photocatalytic reaction test and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–Vis diffuse reflectance spectra (DRS). The results showed that fluorine was successfully doped into the TiO₂ hemispheres. The F-doped TiO₂ hemispheres showed high visible light activity in degradation of acid orange II, which could be attributed to the creation of oxygen vacancies and good crystallinity.     

Photocatalytic reduction of methylene blue by TiO2 nanotube arrays: effects of TiO2 crystalline phase

TiO₂ nanotube arrays were synthesized by anodization of Ti metal sheets followed by thermal annealing at elevated temperatures from 400 to 600 °C. Scanning electron microscopic measurements showed that dense arrays of nanotubes were produced with the inner diameter about 100 nm, wall thickness 35 nm, and length about 10 μm. X-ray diffraction measurements showed that the as-prepared nanotubes were largely amorphous, whereas thermal annealing led to the formation of well-defined anatase crystalline phase. More interestingly, at 470 °C, the brookite crystalline phase also started to emerge, which became better defined at 500 °C and disappeared eventually at higher temperatures, a phenomenon that has not been observed previously in TiO₂ nanotube arrays prepared by anodization. The impacts of the TiO₂ nanocrystalline structure on the photocatalytic activity were then examined by using the reduction of methylene blue in water as an illustrating example. Upon exposure to UV lights, the visible absorption profiles of methylene blue exhibited apparent diminishment. Based on these spectrophotometric measurements, the corresponding pseudo-first-order rate constant was estimated, and the sample thermally annealed at 500 °C was found to exhibit the highest activity. The strong correlation between the TiO₂ crystalline characteristics and photocatalytic performance suggests that the synergistic coupling of the anatase and brookite crystalline domains led to effective charge separation upon photoirradiation and hence improved photocatalytic activity, most probably as a consequence of the vectorial displacement at the nanoscale junctions between these crystalline grains that impeded the dynamics of electron–hole recombination. These results demonstrate the significance of nanoscale engineering in the manipulation of oxide photocatalytic performance.