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.     

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.     

Application of immobilized nanotubular TiO(2) electrode for photocatalytic hydrogen evolution: reduction of hexavalent chromium (Cr(VI)) in water

In this study, immobilized TiO(2) electrode is applied to reduce toxic Cr(VI) to non-toxic Cr(III) in aqueous solution under UV irradiation. To overcome the limitation of powder TiO(2), a novel technique of immobilization based on anodization was applied and investigated under various experimental conditions. The anodization was performed at 20V-5 degrees C for 45min with 0.5% hydrofluoric acid, and then the anodized samples were annealed under oxygen stream in the range 450-850 degrees C. Based on the results of the experiments, the photocatalytic Cr(VI) reduction was favorable in acidic conditions, with approximately 98% of the Cr(VI) being reduced within 2h at pH 3. Among the samples tested under same anodizing condition, the nanotubular TiO(2) annealed at 450 and 550 degrees C showed highest reduction efficiencies of Cr(VI). In addition, the surface characterizations (zeta potential, XRD, and SEM) of these samples proved that the Cr(VI) reduction efficiency was higher under acidic conditions and at a lower annealing temperature. From this research, it was concluded that the anodized TiO(2) has the potential to be a useful technology for environmental remediation as well as photocatalytic hydrogen production from water.     

热处理工艺对多孔TiO2薄膜光催化性能的影响

以十八胺为模板剂,采用溶胶-凝胶法在玻璃基体上制备了多孔TiO2薄膜,研究了热处理工艺对薄膜理化性质及光催化性能的影响。随煅烧温度和煅烧时间的增加,TiO2薄膜表面逐渐形成清晰的孔结构,晶粒尺寸增大。薄膜由锐钛矿型TiO2组成,Ti以Ti 4+的形式存在。制备的TiO2薄膜厚度在200nm左右,薄膜的UV-Vis透射率随煅烧温度的升高呈下降趋势,随煅烧时间的延长先下降而后又上升。多孔TiO2薄膜光催化降解甲基橙结果表明,随煅烧温度升高薄膜的光催化活性增加,在500℃煅烧2h制备的薄膜具有最佳的光催化活性。     

Effect of filler types and calcination temperature on the microstructure and the nitric oxide photocatalytic activity of composite titanium dioxide films

The composite titanium dioxide (TiO(2)) films coating on the woven glass fabric were prepared by a modified sol-gel process, using pre-calcinated TiO(2) nanoparticle or silica gel as filler. The characterized physicochemical properties of the prepared catalyst films showed that the specific surface area, the microstructure and the crystal structure of the catalysts were greatly affected by the fillers and the calcination temperature. The physicochemical properties of composite films and the photocatalytic activity of nitric oxide (NO) show that the pre-calcinated TiO(2) nanoparticle is more favorable than silica gel as filler. The pre-calcinated TiO(2) nanoparticle filler can increase the photocatalytic activities of the catalysts by increasing the specific surface area, introducing a bimodal mesoporous structure, and creating a polymorphous crystal structure. And the TiO(2)-TiO(2) film calcinated at 400 degrees C exhibits the highest photocatalytic activity for NO oxidation and is more active than Degussa P25.     

Synthesis, characterization and photocatalytic H2 generation over ternary indium titanate nanoparticles

A low temperature surfactant-free solution-phase method has been successfully developed for the synthesis of ternary In2TiO5, nanoparticles using a solvothermal route. The mechanistic aspects of synthesis of In2TiO5 nanoparticles from precursors, In(acac)3 and Ti(IV) isopropoxide in benzyl alcohol at 220 degrees C under solvothermal conditions, were investigated by GC-MS and 13C{1H} NMR analysis. The N2-BET surface area of the 5-8 nm sized In2TiO5 nanoparticles was found to be 60 m2 g(-1), which decreased with increase in calcination temperature; 38 m2 g(-1) at 800 degrees C; 5 m2 g(-1) at 1200 degrees C. The High resolution transmission electron microscopy (HR-TEM) shows well-developed lattice fringes of the crystalline nanoparticles, and selected area electron diffraction (SAED), pattern was indexed to be orthorhombic In2TiO5. The nanoparticles show better photocatalytic hydrogen generation from water-methanol mixtures over bulk In2TiO5, anatase TiO2 nanoparticles prepared by identical route and commercial TiO2 photocatalyst (Degussa, P25) under UV-visible irradiation (16% UV + 84% visible). Photocatalytic properties as a function of crystallinity and surface area of indium titanate nanoparticles have also been investigated. The high photoactivity obtained is correlated with the electronic and crystal structure of In2TiO5.     

Formaldehyde degradation by photocatalytic Ag-doped TiO2 film of glass fiber roving

The photocatalytic Ag doped TiO2 porous films were prepared by sol-gel method and dip coated on glass fiber roving. The sol composed of titanium (IV) isopropoxide, triethanolamine, ethanol and nitric acid followed by calcination of the film at 500 degrees C for 1 hour with a heating rate of 3 degrees C/min. The surface morphology and properties of synthesized TiO2 films were characterized by X-ray diffraction, atomic forced microscope and scanning electron microscope. A laboratory photocatalytic reactor was set up to carry out photoactivity of the prepared catalysts. The results show that TiO2-Ag and TiO2-Ag-TEA porous films give highest rate of formaldehyde gas degradation. It can be noted that triethanolamine exhibits two effects on TiO2 composite films; one is its effect on porous film structure and second is a reverse effect of hindrance of anatase growth.     

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.     

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.     

Aqueous Cr(VI) photo-reduction catalyzed by TiO2 and sulfated TiO2

TiO(2) and sulfated TiO(2) (SO(4)(2-)/TiO(2)) catalysts with different textural properties were prepared under different calcination temperatures and the photo-reduction of Cr(VI) to Cr(III) catalyzed by these catalysts was investigated. For the photocatalytic reduction of Cr(VI), the photocatalytic activities of the TiO(2) samples were found to be strongly dependent of the calcination temperature and TiO(2) calcined at 400 degrees C showed a higher catalytic activity compared to other TiO(2) catalysts. In contrast, sulfation of TiO(2) stabilized the catalytic activities of SO(4)(2-)/TiO(2) catalysts. At low calcination temperature, SO(4)(2-)/TiO(2) catalysts exhibited catalytic activities almost comparable with that of TiO(2) and the catalytic activities of SO(4)(2-)/TiO(2) catalysts were markedly higher than TiO(2) under high calcination temperature. In addition, the removal of surface SO(4)(2-) of SO(4)(2-)/TiO(2) catalyst led to a marked decrease of the catalytic activity for Cr(VI) photo-reduction, suggesting that the presence of surface SO(4)(2-) provided an acid environment over the catalyst surface and favored the photo-reduction of Cr(VI).     

Direct formation of reusable TiO2/CoFe2O4 heterogeneous photocatalytic fibers via two-spinneret electrospinning

A reusable photocatalytic TiO2/CoFe2O4 composite nanofiber was directly formed by using a vertical two-spinneret electrospinning process and sol-gel method, followed by heat treatment at 550 degrees C for 2 h. The high photocatalytic activity of the composite nanofibers depends on the good morphology of the fibers and the appropriate calcination temperature. The crystal structure and magnetic properties of the fibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). The photocatalytic activity of the TiO2/CoFe2O4 fibers was investigated through ultraviolet-visible absorbance following the photo-oxidative decomposition of phenol. Meanwhile, the presence of CoFe2O4 not only broadens the response region of visible light, but also enhances the absorbance of UV light. Furthermore, these fibers displayed photocatalytic activity associated with magnetic activity of CoFe2O4 ferrites, allowing easy separated of the photocatalysts after the photo-oxidative process and effectively avoided the secondary pollution of the treated water.     

Synthesis of mesoporous anatase TiO2 nanotubes by a hydrothermal treatment and their use in solid-state dye-sensitized solar cells

Mesoporous anatase TiO2 nanotubes (NTs) with the diameter of about 7 12 nm and the length of several hundred nanometers were synthesized by a hydrothermal method on commercial TiO2 particles in NaOH followed by HCI washing. The samples were characterized by X-ray diffraction (XRD), transmitting electron microscopy (TEM), and Brunauer-Emmet-Teller (BET) measurements. The hydrothermal treatment temperature at 130 degrees C was shown to affect not only the extent of particle-to-sheet conversion, and thus the resulting structures of the NTs, but also the anatase-to-rutile transformation. The surface area of the NTs was 200 m2g(-1). This value was much higher in comparison to TiO2 nanoparticles of 50 m2g(-1). It was also found that the NT photoelectrodes had a pronounced impact on the performance of solar cells as compared to nanoparticle ones. This was probably due to lead to a significantly higher specific dye loading and, for certain hydrothermal treatments, resulting in a doubling of the solar cell efficiency (in our case from 2.84% to 4.03% of AM 1.5 conditions).     

Effects of structure of anodic TiO(2) nanotube arrays on photocatalytic activity for the degradation of 2,3-dichlorophenol in aqueous solution

In this study titanium dioxide nanotube (TNT) arrays were prepared by an anodic oxidation process with post-calcination. The morphology and structure of the TNT films were studied by field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the TNT films was evaluated in terms of the degradation of 2,3-dichlorophenol in aqueous solution under UV light irradiation. The effects of the nanotube structure including tube length and tube wall thickness, and crystallinity on the photocatalytic activity were investigated in detail. The results showed that the large specific surface area, high pore volume, thin tube wall, and optimal tube length would be important factors to achieve the good performance of TNT films. Moreover, the TNT films calcined at 500 degrees C for 1h with the higher degree of crystallinity exhibited the higher photocatalytic activity than other TNT films calcined at 300 and 800 degrees C. Consequently, these results indicate that the optimization of TiO(2) nanotube structures is critical to achieve the high performance of photocatalytic reaction.     

Effects of substrate temperature on the microstructure and photocatalytic reactivity of TiO2 films

Transmission electronic microscopy is used to study the structure, morphology and orientation of thin TiO2 films prepared by reactive magnetron sputtering on glass slides at different substrate temperatures (100 to 400 °C). The TiO2 films are used to purify a dye in waste water. The microstructure and photocatalytic reactivity of TiO2 films have been shown to be functions of deposition temperature. In the temperature range examined, all film samples have a porous nanostructure and the dimension of particles grown with increasing deposition temperature. Films are amorphous at temperatures of 100 °C and only anatase phase forms at 200 °C and above. Films deposited between 200 to 300 °C show a preferred orientation, while films at 400 °C change into complete random orientation. Deposition at 250 °C yields high efficiency in photocatalytic degradation owing to the high degree of preferred orientation and nanocrystalline/nanoporous anatase phase. © 1998 Kluwer Academic Publishers     

掺铁二氧化钛纳米线的合成及其光催化性能

首次以钛酸丁酯、异丙醇等有机物为原料,在10M NaOH溶液中水解后,于180℃水热24h,一步法合成二氧化钛纳米线(TNWs),并用扫描电子显微镜(SEM)和X射线衍射(XRD)等手段表征其形貌和结构。结果表明,所得TNWs焙烧到950℃时,仍为锐钛矿相,表明本制备方法迟滞了二氧化钛由锐钛矿相到金红石相的转变。此外,以甲基橙为目标降解物,在300 W汞灯照射下,研究了不同水热温度、保温时间及掺杂量对掺铁二氧化钛纳米线(Fe-TNWs)光催化性能的影响。结果表明,于750℃焙烧4h制备的掺铁摩尔百分数为0.5%的TNWs,具有最强的光催化降解性能,其降解速率和效率较未掺杂的样品都有了大幅度的提高。     

Low-temperature Preparation of Photocatalytic TiO2 Thin Films on Polymer Substrates by Direct Deposition from Anatase Sol

Anatase TiO2 sol was synthesized under mild conditions （75℃ and ambient pressure） by hydrolysis of titaniumn-butoxide in abundant acidic aqueous solution and subsequent reflux to enhance crystallization. At room temperature and in ambient atmosphere, crystalline TiO2 thin films were deposited on polymethylmethacrylate （PMMA）, SiO2-coated PMMA and SiO2-coated silicone rubber substrates from the as-prepared TiO2 sol by a dip-coating process. SiO2 layers prior to TiO2 thin films on polymer substrates could not only protect the substrates from the photocatalytic decomposition of the TiO2 thin films but also enhance the adhesion of the TiO2 thin films to the substrates. Field-emission type scanning electron microscope （FE-SEM） investigations revealed that the average particle sizes of the nanoparticles composing the TiO2 thin films were about 35-47 nm. The TiO2 thin films exhibited high photocatalytic activities in the degradation of reactive brilliant red dye X-3B in aqueous solution under aerated conditions. The preparation process of photocatalytic TiO2 thin films on the polymer substrates was quite simple and a low temperature route.     

水热合成单斜晶系BiVO4可见光催化剂及其性能

采用水热法合成了纯单斜晶系的可见光催化剂BiVO4,考察了水热温度、水热时间和体系的pH值对BiVO4结构和光催化性能的影响。利用XRD、SEM、BET和UV-VIS对样品进行了表征,结果表明:获得的BiVO4具有中空棒状结构,升高水热温度、提高反应溶液的pH值、延长水热时间有利于单斜晶系BiVO4的生成。确定了BiVO4的最优合成条件为:水热温度140℃,水热时间6h,反应体系pH=9。选择亚甲基蓝溶液作为光催化降解物质,研究BiVO4的可见光催化性能和催化机理。结果表明,最优条件下制备的BiVO4具有较好的可见光催化性能;同时,增加降解体系的pH值提高了催化剂对亚甲基蓝的吸附能力和活化电子的利用效率,有利于提高BiVO4的光催化性能。     

Effects of mineral tourmaline particles on the photocatalytic activity of TiO2 thin films

Titania composite thin films (T/TiO2) containing tourmaline particles were prepared by a sol-gel method, using alkoxide solutions as precursor. The tourmaline particles and thin films were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and so on. The effects of tourmaline on the photocatalytic activity of TiO2 were measured with methyl orange as an objective photodegradation substance. The results showed that the photocatalytic degradation of methyl orange conformed to the first-order kinetic equation and the composite thin films had better photocatalytic activity due to the cooperation of polarity and the far infrared emission of tourmaline. The T/TiO2 thin films including 0.5 wt% tourmaline exhibited better photocatalytic activity when heat-treated at 250 degrees C for 3 h, than pure TiO2 thin films under the ultraviolet irradiation.     

Chemical vapour deposition of nitrogen-doped titanium dioxide thin films

Nitrogen-doped titanium dioxide is often considered as a promising nanomaterial for photocatalytic applications. Here we report the first results of a study of APCVD of N-doped TiO2 thin films prepared with the use of ammonia as a source of nitrogen and titanium tetraisopropoxide (TTIP) as a source of Ti and O atoms. The obtained films were analyzed with X-ray diffraction, infrared spectroscopy, atomic force microscopy, X-ray photoelectron spectroscopy, UV-Vis spectroscopy, and ellipsometry. It was found that the film growth rate in the TTIP-NH3-Ar reaction system varied insignificantly with substrate temperature in the range of 450,..., 750 degrees C and did not exceed 4.4 nm/min. Yellow and orange layers with nitrogen content of about 7.6% were formed at the deposition temperature higher than 600 degrees C. The results of the structure analysis of the deposited films showed that addition of ammonia led to stabilization of the amorphous phase in the films. The effect of ammonia on optical and photocatalytic properties was also considered.     

Photocatalytic activities of Ion doped TiO2 thin films when prepared on different substrates

Pure and ion doped TiO₂ thin films were prepared by sol-gel dip coating process on metallic and non-metallic substrates. Test metal ion concentration ranged from 0.000002 to 0.4 at.%. The resulting films were annealed in air and characterized by optical spectroscopy and X-ray diffraction. The photodegradation of methyl orange under UV irradiation by pristine and ion-doped TiO₂ films was quantified in a photocatalytic reactor developed in this study. In general, both doped and undoped TiO₂ crystals appeared in anatase phase and the photocatalytic activities of the TiO₂ thin films varied with substrates, calcination temperature, doping ions and their concentrations. The best calcination temperature for different substrates ranged from 450 to 580 °C. Films prepared on the metallic substrates resulted in higher photocatalytic activities, while ion doping lowered their efficiencies. On the contrary, for non-metallic substrates except ceramic the photocatalytic efficiencies of undoped films were much lower (< 30%), while ion doping was shown to increase the photocatalytic efficiencies remarkably in some cases, e.g., Cr³⁺ with the tile substrate. Overall, ion doping affected the photocatalytic efficiency of TiO₂ films, and an optimal doping concentration of between 0.0002 and 0.002 at.%, close to an estimate by the Debye length equation, resulted in the highest efficiency for most substrates.