Rapid communication Preparation of TiO_2 nanometer thin films with high photocatalytic activity by reverse micellar method

Two kinds of TiO2 nanometer thin films were prepared on stainless steel by the reverse micellar and sol-gel methods, respectively. The calcined TiO2 thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), BET surface area and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity was evaluated by photocatalytic decoloration of methyl orange aqueous solution. The results showed that the TiO2 thin films prepared by reverse micellar method (designated as RM-TiO2 films) showed higher photocatalytic activity than those by sol-gel method (designated as SG-TiO2 films). This is attributed to the fact that the former is composed of smaller monodispersed spherical particles with a size of about 15 nm and possesses higher surface areas.     

TiO2 thin film photocatalyst

It is well known that the photocatalyfic activity of TiO2 thin films strongly depends on the preparing methods and post-treatmaent conditions, since they have a decisive influence on the chemical and physical properties of TiO2 thin films.Therefore, it is necessary to elucidate the influence of the preparation process and post-treatment conditions on the photocatalytic activity and surface microstructures of the films. This review deals with the preparation of TiO2 thin film photocatalysts by wet-chemical methods (such as sol-gel, reverse micellar and liquid phase deposition) and the comparison of various preparation methods as well as their advantage and disadvantage. Furthermore, it is discussed that the advancement of photocatalytic activity, super-hydrophilicity and bactericidal activity of TiO2 thin film photocatalyst in recent years.     

Preparation and photocatalytic activity of composite films containing clustered TiO2 particles and mineral tourmaline powders

The novel composite films containing clustered TiO2 particles and fine tourmaline particles on the surface of copper webs were prepared by the sol-gel method. The microstructures of the composite films were investigated by scanning electron microscopy （SEM）, and the photocatalytic activity of the films was evaluated by photocatalytic degradation of methyl orange, respectively. The results indicate that tourmaline particles can obviously influence the microstructures of TiO2 films and enhance the photocatalytic activity due to their spontaneous permanent polarity and high radiotechnology of far infrared. During preparing the composite films, the clustered TiO2 particles with lots ofnano-sized ladder layers can grow on the surface of fine tourmaline particles, the thickness of ladder layer is 10 nm, and the average diameter ofnano-sized TiO2 particles is 15 nm.     

Effect of substrate temperature on structural properties and photocatalytic activity of TiO2 thin films

Titanium dioxide （TiO2） films with anatase structure were prepared on quartz glass substrates by pulse laser ablating titanium （99.99%） target under oxygen pressure of 10 Pa at substrate temperature of 500-800 ℃. The structural properties of the films were characterized by X-ray difffactometry（XRD）, X-ray photoelectron spectroscopy（XPS） and field emission scan electron microscopy（FESEM）. The results show that, as the substrate temperature is increased from 600 ℃ to 800 ℃, the anatase structure of the films changes from random growth to （211）-oriented growth. The absorption edge tested by UV-Vis Spectrometer has a blue shift. The photocatalytic activity of the films was tested on the degradation of methyl orange. It is found that the film with random growth structure exhibits better photo-degradation efficiency than that with （211）-oriented growth structure.     

溶胶-凝胶法制备TiO2-SiO2系亲水性薄膜的研究

采用溶胶-凝胶(sol-gel)法在陶瓷釉面砖表面制备了TiO2-SiO2系亲水性薄膜.利用XRD、AFM、FTIR、热显微镜润湿角测角仪等,研究了SiO2添加量对薄膜的微结构和亲水性等的影响.结果表明:薄膜中TiO2晶粒尺寸随着SiO2含量的增加而减小;TiO2和SiO2分别单独成相,并有Ti-O-Si键形成,存在部分复合氧化物,在光照条件下,由于取代反应,复合氧化物的表面易形成Lewis酸,薄膜表面吸附的羟基含量增多且稳定,SiO2摩尔分数为0.4时,润湿角小于5°,薄膜的超亲水状态可在停止光照后长时间存在.     

Preparation of CulnSe2 thin films by paste coating

Precursor pastes were obtained by milling Cu-In alloys and Se powders.CuInSe2 thin films were successfully prepared by precursor layers,which were coated using these pastes,and were annealed in a H2 atmosphere.The pastes were tested by laser particle diameter analyzer,simultaneous thermogravimetric and differential thermal analysis instruments (TG-DTA),and X-ray diffractometry (XRD).Selenized films were characterized by XRD,scanning electron microscopy (SEM),and energy dispersive spectroscopy (EDS).The results indicate that chalcopyrite CuInSe2 is formed at 180℃ and the crystallinity of this phase is improved as the temperature rises.All the CuInSe2 thin films,which were annealed at various temperatures,exhibit the preferred orientation along the (112) plane.The compression of precursor layers before selenization step is one oftbe most essential factors for the preparation of perfect CulnSe2 thin films.     

Photocatalytic Property of Nanostructured S Doped TiO2 Films Prepared by the Micro Plasma Method

以钛为基体,在较短的时间内,采用微等离子体氧化法制备了TiO2薄膜。以罗丹明B溶液为目标污染物测试所得TiO2薄膜光催化性能。为提高所得TiO2薄膜的光催化性能,向电解液中添加了不同浓度的CH4N2S,制备S掺杂TiO2薄膜。利用扫描电镜(SEM)、光电子能谱（EDS）和X射线衍射仪（XRD）表征S掺杂前后所得的TiO2薄膜表面形貌、元素组成和晶体结构。结果表明,所得TiO2薄膜为多孔状,孔径大小均一。电解液中的CH4N2S浓度对微孔密度和孔径影响较大,S掺杂能使多孔TiO2微孔密度增大, 比表面积增大。但S对TiO2晶相组成影响不大,对晶胞参数有所影响。S掺杂可有效提高TiO2的光催化活性, 其中当电解液中的CH4N2S为6.0 g/L时,对初始浓度为10 mg/L罗丹明B溶液120 min的降解率可达到98%, 表现出最强的光降解能力。     

溶胶——凝胶工艺制备的TiO2纳米薄膜及其表面结构

采用溶胶—凝胶工艺在玻璃表面制备了均匀透明的锐钛矿型ＴｉＯ２ 纳米薄膜， 其颗粒大小在４０ ～８０ ｎｍ 。薄膜的Ｘ 射线衍射分析表明， 当薄膜的厚度小于０ ．４５ μｍ 时， 薄膜中未出现明显的锐钛矿的衍射峰。Ｘ 射线光电子能谱（ＸＰＳ） 和电子自旋共振谱（ＥＳＲ） 的实验结果表明： 薄膜中除含有Ｔｉ， Ｏ 元素外， 还有一定量的来自有机前驱物中未完全燃烧的碳和少量从玻璃表面扩散到薄膜中的Ｎａ 和Ｃａ 元素； Ｔｉ 元素除了以＋ ４ 价形式存在外， 还有一定量的Ｔｉ 以＋ ３ 和＋ ２ 价形式存在。ＴｉＯ２ 薄膜在５３０ ｎｍ附近的宽吸收带也证实了ＴｉＯ２ 薄膜中低价钛元素的存在。     

Deposition of photocatalytic TiO2 and N-doped TiO2 films by arc ion plating

TiO2 and N-doped TiO2 films were deposited on the glass substrates by arc ion plating method. The results show that the deposition rate does not change with the increasing deposition time. The increase of mass flow rate of N2 gives rise to the increase of deposition rate. All as-deposited TiO2 and N-doped TiO2 films are amorphous. The anatase TiO2 phase with preferred orientation （101） is acquired by post-annealing at 400 ℃ for 2 h. The incorporation of N into the TiO2 films and the heat treatment extensively shift the band edge to the visible light region.     

单分散纳米TiO2光催化剂的水解-溶胶制备法

以Ti(SO4)2为原料，在一定温度下直接水解、胶溶、加入晶种、熟化，制备出单分散性、热稳定性良好、平均粒径在22nm左右、比表面积在80m^2／g以上的TiO2纳米微粒。研究了Ti(SO4)2浓度、水解时间及晶种对纳米微粒粒径的影响。对样品进行了TG-DTA，XRD和SEM分析。结果表明：样品经真空冷冻干燥后，TiO2粉体主要为锐钛矿型，且随焙烧时间增加和温度升高，其金红石型含量显著增多，粉体粒径也有一定增大，但在不同的温度区间粒径增长速率有较大的区别。     

Photocatalytic degradation characteristic of amorphous TiO2-W thin films deposited by magnetron sputtering

TiO2-W films were deposited on the slides by reactive magnetron sputtering. Properties of the films were analyzed via AFM, XRD, XPS, STS, UV-Vis and ellipse polarization apparatus. The results show that TiO2-W films are amorphous. The AFM map reveals that the surface of the film is tough and porous. The experiments of decomposing methylene blue indicate that the thickness threshold on these films is 141 nm, at which the rate ofphotodegradation is 90% in 2 h. And when the thickness is over 141 ran, the rate of photodegradation does not increase any more. This result is completely different from that of crystalloid TiO2 thin film.     

磁控溅射TiO2薄膜的相结构转变温度

利用射频磁控溅射制备了TiO2致密薄膜,并通过退火处理实现TiO2的相转变,采用扫描电镜,X射线衍射等手段对薄膜相结构进行表征并做了详细的分析,结果表明,退火后TiO2薄膜结构致密,表面呈现出大小均匀的纳米晶粒。400 ℃退火时,TiO2薄膜为单一的锐钛矿相,500～600 ℃退火时为锐钛矿和金红石混合相,700 ℃以上退火时则完全转变为金红石相。     

Effects of tourmaline on microstructures and photocatalytic activity of TiO2/SiO2 composite powders

The SiO2/TiO2 composite powders including mineral tourmaline powders （T/SiO2/TiO2） were prepared from a sol made by a two-step hydrolysis method, using metasilicate ester as precursor. The powders were characterized by scanning electron microscopy （SEM）. The photocatalytic activity of the sample was evaluated by the photocatalytic degradation of methyl orange. The effects of heat-treatment on the photocatalytic activity were discussed. It is found that the T/SiO2/TiO2 composite powders show higher photocatalytic activity when including 10% SiO2 and 4% tourmaline. Moreover, the photocatalytic mechanism of tourmaline on the powders was proposed.     

Preparation and oxygen-sensing properties of TiO2 porous thin films on alumina substrate

The titanium dioxide sols were synthesized with tetrabutyl titanate as precursor, diethanolamine（DEA） as complexing agent , polyethylene glycol （PEG） as organic template. The porous films were prepared by sol-gel method, The structures and morphology of the titanium dioxide porous films were characterized by FE-SEM. The formation mechanism of TiO2 porous films and the relation between the porous structure and oxygen-sensing properties of TiO2 films were studied. Ordered structure was formed by assembling between TiO2 colloid particles and the template molecules. PEG molecules acted on TiO2 colloid particles by hydrogen bond and bridge oxygen. The porous structure was formed after the organic template was decomposed when calcining the films. The diameter, amount and distribution of the pores in the films are related with the content of PEG. The pore diameter increases with increasing of content of PEG and the pore density reaches the maximum at certain content. Oxygen-sensitivity and response speed of porous TiO2 films are improved compared with films without pores. Both the sensitivity and response speed increase with the increasing of pore diameter and pore density. Oxygen-sensitivity reaches 3 order of magnitude at 800 ℃. Its response time from H2/N2 to O2/N2 atmosphere and vice versa is about 0.11 s and 0.12 s respectively. Although the sensitivity and response speed increase, the resistance-temperature properties of porous films are not notably improved with the increasing of the content of PEG.     

用TiCl4制备纳米TiO2的研究状况

综述了以TiCl4为原料制备纳米TiO2的主要方法:氢氧火焰水解法、气相氧化法、气相燃烧法、液相沉淀法、溶胶-凝胶法、微乳液法和水热法,并对其优缺点做了相应的评论,最后指出了今后研究的方向。     

光催化二氧化钛薄膜的制备工艺研究进展

评述了制备二氧化钛薄膜的液相法、气相法和电化学法3大类方法的优缺点，以及3大类方法所包含的溶胶-凝胶、微乳液、磁控溅射、物理气相沉积、化学气相沉积、阳极氧化和微弧氧化等方法制备二氧化钛薄膜的工艺步骤、特点及研究进展。文章最后指出，液相法由于自身存在的优点，仍将是今后二氧化钛薄膜制备和研究的重点；而光催化性能更好的掺杂二氧化钛，其研究重点是探讨掺杂方式、制备方法和优化配比等。     

Effect of surfactants on preparation of nanometer TiO2 by pyrohydrolysis

The nanometer TiO2 was prepared by pyrohydrolysis with titanic solution.The effects of species and content of the surfactants on the particle size,morphology and phase of TiO2 were studied by using LPA,XRD and TEM respectively.The results show that it is beneficial to reducing the aggregation of TiO2 particles with adding surfactants to the solution.Nanometer TiO2 powders with the size of 40-55 nm are obtained by adding the anion surfactants in the optimal content of 1.5%(mass fraction).The effect of cationic surfactant for reducing particle aggregation is not as good as that of anion.The crystal phase constitutent of TiO2 is dependent on the temperature of thermal treatment and complete anatase can be achieved after calcining in the temperature range of 350-750℃.     

Micro-porous TiO2 thin films grown on surface of Ti substrate

Microporous titanium dioxide thin films have been grown on titanium plates by the micro-plasma oxidation method with different current densities (4, 6, 10 and 14 A/dm2). X-ray diffraction, scanning electronic microscopy and UV-Vis spectrophotometry were used to characterize the films. It is found that the films grown are microporous and consist of crystalline titanium dioxide. The micropore size and the content of anatase and rutile TiO2 phase increase with the applied voltage. The relatively higher degradation efficiency for rhodamine B is obtained in the film produced with a current density of 10 A/dm2.