Low-temperature preparation and characterization of iron-ion doped titania thin films

Iron-ion doped titania thin films with an anatase phase were successfully synthesized in this study using the high-pressure crystallization (HPC) process. The crystallization temperature of Fe(3+)-doped TiO(2) thin films was markedly reduced to be as low as 125 degrees C. The films prepared via the HPC process have a more uniform microstructure and smaller grain sizes than the films prepared via the atmospheric-pressure annealing process. The films prepared via both processes were found to have photocatalytic properties under visible light. The films prepared via the HPC process exhibited enhanced photocatalytic activities in comparison with the films annealed via the conventional process. Increasing the annealing temperature in the HPC process resulted in an improvement in the photocatalytic properties because of an increase in the crystallinity of the prepared films. The HPC process was demonstrated to be a potential method for synthesizing visible-light driven titania thin films with enhanced photocatalytic activities at low temperatures.     

Photocatalytic Property of TiO2 Films Deposited by Pulsed DC Magnetron Sputtering

TiO2 thin films were prepared by DC magnetron sputtering with the oxygen flow rate higher than the threshold. The film deposited for 5 h was of anatase phase with a preferred orientation along the <220> direction, but the films deposited for 2 and 3 h were amorphous. The transmittance and photocatalytic activity of the TiO2 films increased constantly with increasing film thickness. When the annealing temperature was lower than 700℃, only anatase grew in the TiO2 film. TiO2 phase changed from anatase to rutile when the annealing temperature was above 800℃. The photocatalytic activity decreased with increasing annealing temperature.     

溶胶凝胶法制备的TiO2薄膜结构对光催化活性的影响

TiO2多孔纳米薄膜采用溶胶－凝胶法在普通载玻片上制得。薄膜的结构如孔径、孔分布和厚度可控制。通过稀醋酸的分解来测定锐钛矿TiO2多孔薄膜的结构对光催化活性的影响。     

TiO2/SiO2复合薄膜的晶化特征和结构转变研究

对TiO2／SiO2复合薄膜的晶化特征进行了分析，研究表明，随着TiO2含量的增加，其晶化温度降低，而由锐钛矿相完全转变为金红石相的速度减慢．SiO2的析晶温度也随着TiO2含量的增加而降低，即TiO2具有诱导SiO2析晶的作用．锐钛矿晶粒尺寸的增加幅度随着TiO2含量的降低和热处理温度的升高而增大．其晶粒尺寸的大小与热处理时间的平方根成正比．认为由于TiO2含量的不同，造成薄膜中由锐钛矿相完全转变成金红石相的速度差异主要来自于薄膜中应力的作用．     

Photocatalytic degradation of methyl orange: influence of H2O2 in the TiO2-based system

The purpose of this study was to investigate the photocatalytic oxidation of a reactive azo dye. The photocatalytic activity of the TiO2 was studied using a reactor equipped with UV-A sources, with maximum emission at 365 nm. The photocatalytic activity of the TiO2 powder (99.9% anatase) and thin films has been measured through the decomposition of methyl orange solutions. The thin film was prepared by doctor blade and spray pyrolysis deposition (SPD). The TiO2 suspensions were prepared at 1 g/L concentration, and the initial methyl orange concentration was fixed at 7.8125 mg/L. The influence of the TiO2 (powder or thin films) and/or O2 and H2O2 on the photobleaching rate, was tested under different experiments, at pH = 5. Thin films (doctor blade) of TiO2 formed of mezo-sized aggregates formed of nanosized anatase crystallites show better photobleaching efficiency than thin film (SPD) due to their large internal surface. The rate is even higher in H2O2 compared to oxygen environment.     

Surface structure of the TiO2 thin film photocatalyst

Control of the surface structure of titanium dioxide thin film photocatalysts was successfully carried out by a polymer-doped dip-coating process. The thin films prepared were either transparent or opaque, depending on the molecular weight of the polymer doped. All the thin film photocatalysts had anatase form with similar crystallinity. The surface of the transparent thin films looked plain consisting of uniformly aggregated nanometer-size TiO2 particles, while the opaque thin films were formed of cubic crystalline TiO2 at the micrometer level. Both the transparent and opaque films showed catalytic activity for the elimination of NOx in air. The specific surface area and photocatalytic activity of the transparent thin film was almost the same as that of the opaque one. The activity of the thin films was almost equal to the commercial photocatalyst P25. Decrease in the film thickness led to a decrease of the elimination of NO in air by the thin films. The thin films were porous and the surface area was dependent on the film thickness. Adsorbed NO was photooxidized to NO2 by the thin films, while the NO2 formed was re-photooxidized to HNO3 before the desorption of NO2 from the film surface.     

Ti靶及TiO2靶溅射TiO2薄膜微观形貌、结构及光学性质研究

利用射频磁控溅射技术通过Ti靶及TiO2靶在氩氧气氛中同时溅射制备TiO2薄膜,并对所得的样品进行不同温度的退火处理。采用X射线衍射、扫描电子显微镜、拉曼光谱和吸收谱研究了不同的靶材及退火温度对TiO2薄膜晶体结构、微观形貌及光学性质的影响。结果表明:由于靶材的不同,Ti靶溅射时氧分压较低,造成薄膜中存在大量的氧缺陷,晶相发育不完善,颗粒相比TiO2靶溅射时较小,从XRD和拉曼光谱来看,Ti靶溅射得到的TiO2薄膜更有利于金红石相的形成。薄膜的透过率随退火温度的升高而降低,TiO2靶材溅射的薄膜的光学带隙随温度升高而明显降低,而Ti靶得到的薄膜的光学带隙对退火温度的依赖关系不明显。     

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.     

DBD-CVD法制备掺氮二氧化钛薄膜及其结构性能

采用介质阻挡放电化学气相沉积(DBD-CVD)法制备TiO2透明自清洁功能薄膜,选用四异丙醇钛(TTIP)、NH3作为反应先驱体,另外再加入一定量的N2、Ar或者He作为稀释气体控制气体的流量和流速。通过对其进行X射线衍射、紫外-可见光谱、X光电子能谱、场发射扫描电镜、光催化性质、光亲水性质等测试表明,过DBD-CVD方法制备TiO2薄膜,只存在锐钛矿相,氮掺杂改变了薄膜中锐钛矿相晶粒生长的取向,从而影响薄膜的表面微观结构,促使光吸收限红移,提高了薄膜在可见光照射下的光催化效率,并改善了薄膜表面的亲水性能。     

热处理温度对TiO2/SiO2复合气凝胶光催化性能的影响

采用溶胶–凝胶法在常压下经不同温度热处理制备了TiO2/SiO2复合气凝胶光催化剂,利用XRD、TGA和BET等手段对其微观结构进行表征,以甲基橙溶液光催化降解实验评价其光催化性能,研究了热处理温度对TiO2/SiO2复合气凝胶的微观结构及光催化性能影响规律.结果表明:随着热处理温度升高,TiO2/SiO2复合气凝胶中锐钛矿结晶度升高,晶粒尺寸增大,比表面积减小,使TiO2/SiO2复合气凝胶对甲基橙溶液的光催化降解活性呈现先升后降的变化趋势.当热处理温度为700℃左右,紫外光照20 min TiO2/SiO2复合气凝胶对甲基橙溶液的降解率达到95.4%.     

Annealing dependence of residual stress and optical properties of TiO2 thin film deposited by different deposition methods

Titanium oxide (TiO(2)) thin films were prepared by different deposition methods. The methods were E-gun evaporation with ion-assisted deposition (IAD), radio-frequency (RF) ion-beam sputtering, and direct current (DC) magnetron sputtering. Residual stress was released after annealing the films deposited by RF ion-beam or DC magnetron sputtering but not evaporation, and the extinction coefficient varied significantly. The surface roughness of the evaporated films exceeded that of both sputtered films. At the annealing temperature of 300 degrees C, anatase crystallization occurred in evaporated film but not in the RF ion-beam or DC magnetron-sputtered films. TiO(2) films deposited by sputtering were generally more stable during annealing than those deposited by evaporation.     

Solar-light photoamperometric and photocatalytic properties of quasi-transparent TiO2 nanoporous thin films

Transparent photocatalytic surfaces are of ever increasing importance for many applications on self-cleaning windows and tiles in everyday applications. Here, we report the formation and photocatalytic testing of a quasi-transparent thin and nanoporous titania films deposited on glass plates. Sputtered Ti thin films were anodized in fluoride-ion-containing neutral electrolytes to form optically semitransparent nanoporous films, which transformed to be completely transparent after thermal annealing. The nanoporous films were studied at different stages, such as before and after anodization, as well as after thermal annealing using scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis and Raman spectroscopy. It was observed that anodization at 20 V of high-temperature deposited titanium films resulted in regular nanopore films with pore diameters of 30 nm. Structural investigations on the transparent nanopore arrays reveal the presence of anatase phase TiO(2) even after annealing at 500 °C, which was confirmed by XRD and Raman spectroscopy measurements. The solar-light induced photocatalytic decomposition of stearic acid and photoconductivity characteristics of these nanoporous thin films are also presented.     

HNO3处理对TiO2纳米薄膜的光催化活性和表面微结构的影响

通过sol-gel工艺分别在钠钙玻璃和预涂SiO2涂层的钠钙玻璃基体上制备了TiO2光催化纳米薄膜．然后用1mol／L HNO3水溶液对煅烧后的薄膜进行酸处理。用X射线光电子能谱(XPS)、扫描电镜(SEM)和紫外可见光谱(UV—VIS)对酸处理前后TiO2纳米薄膜进行了表征。用甲基橙水溶液的光催化脱色来评价TiO2薄膜的光催化活性。结果表明：SiO2涂层能有效阻止钠离子从玻璃基体向TiO2薄膜的扩散，普通玻璃表面的TiO2纳米薄膜经HNO3处理后，薄膜的光催化活性明显增强。这是由于TiO2纳米薄膜中的钠离子浓度降低以及表面羟基含量增加的缘故。     

Structure, wettability and photocatalytic activity of CO(2) laser sintered TiO(2)/multi-walled carbon nanotube coatings

Nanocomposites of titanium dioxide (TiO(2)) and multi-walled carbon nanotubes (MWNTs) were prepared and deposited by sol-gel spin coating on borosilicate substrates and sintered in air at 300?°C for 15?min. Further irradiation of the films with different CO(2) laser intensities (4.3-17?W?m(-2)) was carried out in order to crystallize TiO(2) in the anatase form while preserving the MWNT's structure. The laser irradiation changed the crystal structure of the coatings and also affected the wettability and photocatalytic activity of the films. The anatase phase was only observed when a minimum laser intensity of 12.5?W?m(-2) was used. The contact angle decreased with the enhancement of the laser intensity. The photocatalytic activity of the films was determined from the degradation of a stearic acid layer deposited on the films. It was observed that the addition of carbon nanotubes themselves increases the photocatalytic activity of TiO(2) films. This efficiency is even improved when high CO(2) laser intensities are used during the sintering of the coatings.     

直流反应溅射TiO2薄膜的制备及其性能研究

采用直流反应磁控溅射的方法,溅射高纯钛靶在ITO石英衬底上制备了TiO2薄膜.用XRD、Raman光谱、AFM和紫外-可见光分光光度计分别测试了TiO2薄膜的结构、表面形貌和紫外-可见光透射谱,研究了工艺因素中溅射气压、氧氩比和退火温度对薄膜结构的影响.采用C(胶)/TiO2/ITO三层结构研究了锐钛矿TiO2薄膜的紫外光响应.实验结果表明较低的溅射气压、合适的氧氩比和较高的退火温度有利于锐钛矿TiO2薄膜的结晶.在2 V的偏压下,锐钛矿TiO2薄膜的紫外光响应上升迟豫时间约为3 s,稳定光电流可达到2.1 mA,对紫外光的灵敏性和稳定的光响应表明TiO2薄膜有可能成为一种新的紫外光探测器材料.     

稀土掺杂TiO2光催化材料的制备和性能

采用溶胶-凝胶法制备了5种稀土（Pr、Nd、Sm,Eu、Dy）掺杂TiO2光催化薄膜,研究了稀土掺杂量,镀膜层数、烧结温度和烧结时间对光催化活性的影响．结果表明,各因素对材料的催化活性均存在一最佳值．薄膜中仅含TiO2而未见稀土氧化物,除掺锴TiO2薄膜完全由金红石相组成外,其余均由锐钛矿相和金红石相的混晶组成,其中金红石相所占比例较大,薄膜表面均存在大量缺陷;稀土掺杂TiO2薄膜对罗丹明B的光降解率可达89．3％．稀土掺杂TiO2显著提高了TiO2对可见光的响应能力,提高了材料的光催化活性．     

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     

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.     

Photocatalytic TiO(2) deposition by chemical vapor deposition

Dip-coating, spray-coating or spin-coating methods for crystalline thin film deposition require post-annealing process at high temperature. Since chemical vapor deposition (CVD) process is capable of depositing high-quality thin films without post-annealing process for crystallization, CVD method was employed for the deposition of TiO(2) films on window glass substrates. Post-annealing at high temperature required for other deposition methods causes sodium ion diffusion into TiO(2) film from window glass, resulting in the degradation of photocatalytic efficiency. Anatase-structured TiO(2) thin films were deposited on window glass by CVD, and the photocatalytic dissociation rates of benzene with CVD-grown TiO(2) under UV exposure were characterized. As the TiO(2) film deposition temperature was increased, the (112)-preferred orientations were observed in the film. The (112)-preferred orientation of TiO(2) thin film resulted in a columnar structure with a larger surface area for benzene dissociation. Obviously, benzene dissociation rate was maximum when the degree of the (112) preferential orientation was maximum. It is clear that the thin film TiO(2) should be controlled to exhibit the preferred orientation for the optimum photocatalytic reaction rate. CVD method is an alternative for the deposition of photocatalytic TiO(2).     

Preparation of re-usable photocatalytic filter for degradation of Malachite Green dye under UV and vis-irradiation

Sn(4+) doped and undoped nano-TiO(2) particles easily dispersed in water were synthesized without using organic solvent by hydrothermal process. Nanostructure-TiO(2) based thin films were prepared on flyswatter substrate, made with stainless steel, by dip-coating technique. The structure, surface and optical properties of the particles and thin films were characterized by element analysis and XRD, BET, SEM and UV/vis/NIR techniques. The photocatalytic performance of the films were tested for degradation of Malachite Green dye in solution under UV and vis-lights. The results showed that the coated flyswatter has a very high photocatalytic performance for the photodegradation of Malachite Green irradiated with UV and vis-lights. The results also proved that the hydrothermally synthesized nano-TiO(2) particles are fully anatase crystalline form and are easily dispersed in water, the coated surfaces are hydrophilic, and the doping of transition metal ion efficiently improved the degradation performance of TiO(2)-coated flyswatter. The photocatalytic performances determined at both irradiation conditions were very good and were almost similar to each other for Sn(4+) doped TiO(2)-coated flyswatter and it can be repeatedly used with increasing photocatalytic activity compared to undoped TiO(2)-coated flyswatter.