Thin films of TiO2:N for photo-electrochemical applications

Dc-pulsed magnetron sputtering from Ti target in reactive Ar+O2+N2 atmosphere was used to grow stoichiometric TiO2:N and non-stoichiometric TiO2-x:N thin films. X-ray diffraction at glancing incidence, atomic force microscopy AFM, scanning electron microscopy SEM, X-ray photoelectron spectroscopy XPS, and optical spectrophotometry were applied for sample characterization. Measurements of photocurrent versus voltage and wavelength over the ultraviolet uv and visible vis ranges of the light spectrum were performed in order to assess the performance of nitrogen-doped titanium dioxide thin films as photoanodes for hydrogen generation in photoelectrochemical cells, PEC. Undoped TiO2 and TiO2-x films were found to be composed of anatase and rutile mixture with larger anatase crystallites (25-35 nm) while the growth of smaller rutile crystallites (6-10 nm) predominated at higher nitrogen flow rates etaN2 as measured in standard cubic centimeters, sccm. Nitrogen-to-titanium ratio increased from N/Ti = 0.05 at etaN2 = 0.8 sccm for stoichiometric TiO2:N to N/Ti = 0.11 at etaN2 = 0.8 sccm for nonstoichiometric TiO2-x:N thin films. A red-shift in the optical absorbance was observed with an increase in etaN2. Doping with nitrogen improved photoelectrochemical properties over the visible range of the light spectrum in the case of nonstoichiometric samples.     

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．     

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．     

Growth of TiO2 with thermal and plasma enhanced atomic layer deposition

We show a comparative study of the TiO2 ALD with TTIP and either O2 or O2-plasma on Si/SiO2 substrates. In particular we compare the surface morphology and crystalline phase by means of Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS) for different O2-plasma procedures upon changing the time between cycles and the N2-purging pressure. The AFM images show that already these parameters may induce structural changes in the TiO2 films grown by ALD, with the formation of crystallites with average lateral width varying between 15 and 80 nm. By means of XAS we also found that the crystallites have mixed anatase and rutile crystalline phases and that smaller crystallites have a greater rutile component than the larger ones.     

氢氧焰燃烧合成核壳结构纳米 TiO2/SiO2复合颗粒及机理分析

利用多重射流氢氧焰燃烧反应器，通过控制进料方式，以TiCl4和SiCl4为原料合成了具有典型核壳结构的纳米TiO2／SiO2复合颗粒，并分析了氢氧焰燃烧合成过程中核壳结构的形成机理．在纳米TiO2／SiO2复合颗粒中，无定形的SiO2均匀地包覆在晶态TiO2颗粒表面形成核壳结构，引入SiO2不但有效抑制TiO2晶粒的生长，而且抑制了锐钛相向金红石相的转变．在TiCl4和SiCl4次序进料时，TiCl4优先反应并通过成核生长生成TiO2纳米颗粒，SiCl4反应生成的SiO2通过在TiO2颗粒表面非均相成核生长，形成核壳结构的纳米复合颗粒．     

Effects of TiO2 nanorod length and post-annealing on the electrical properties of TiO2 nanobarbed fiber structures

TiO2 nanobarbed fiber (NBF) structures consisting of TiO2 nanorods (NRs) on TiO2 nanofibers (NFs) were fabricated. The mean length and diameter of the TiO2 NRs grown for 6 h was 1.38 microm and 71 nm, respectively. One NR was connected to other NRs and the junction points between the TiO2 NRs increased with increasing TiO2 NR length. The crystal structure of the TiO2 NFs and NRs was rutile and anatase, respectively. After post-annealing, only the intensity of the TiO2 NBF peaks increased without any significant structural changes. Raman spectroscopy showed that the TiO2 NBF structure consisted of anatase (TiO2 NFs) and rutile (TiO2 NRs). The bandgap of the TiO2 NBF structure prepared during a TiO2 NR growth time from 0 to 6 h decreased from 3.23 eV to 3.10 eV. The conductivity of the TiO2 NBFs with longer NRs was enhanced by post-annealing.     

Preparation and photocatalytic activity of nanoglued Sn-doped TiO2

In this paper, Sn-doped TiO(2) photocatalyst was prepared and immobilized on a glass substrate using an about-to-gel SiO(2) sol as a nanoglue. The characterization of the Sn-doped TiO(2) by XRD showed that 5% Sn content is formed by anatase and rutile crystallites. Characterization of the nanoglued photocatalyst by the BET measurement, TEM, and SEM showed that the photocatalyst was a nanoporous material with a high-surface area. The Sn-doped TiO(2) was uniformly dispersed within the three-dimensional network of the silica in the form of nanoparticles. The nanoglued photocatalyst showed high photocatalytic activity during the degradation of penicillin under UV light. The effect of different Sn content on the amount of hydroxyl radical was discussed by using salicylic acid as probe molecules. The results show that an appropriate amount of Sn dopant can greatly increase the amount of hydroxyl radicals generated by TiO(2) nanoparticles, which are responsible for the obvious increase of photocatalytic activity.     

Evaluation of microwave plasma sintering for the fabrication of dye sensitized solar cell (DSSC) electrodes

Dye-sensitized solar cells (DSSCs) have demonstrated considerable potential due to their solar energy conversion efficiency and their fabrication from relatively low cost materials. Titanium dioxide (TiO2) nanoparticles are widely used in the fabrication of the DSSC electrodes. There is a considerable energy requirement however required for the sintering of the TiO2 particles during the fabrication of the mesoporous electrodes. This study investigates the use of microwave (MW) plasma treatments as a rapid, energy efficient processing technique for the sintering of the metal oxide particles. A comparison is made with conventional furnace treatments for the sintering of TiO2 nanoparticles (Degussa P25), deposited onto fluorine doped tin oxide (FTO) coated glass substrates. Subsequent to the TiO2 sintering, ruthenium based dye (N719) adsorption studies were carried out for coatings heated using both sintering techniques. Based on UV/Vis absorption spectra measurements of 5 mins plasma and 30 mins furnace sintering, it was observed that both sintering techniques exhibited similar levels of dye adsorption. A decrease in the level of dye adsorption was observed for the TiO2 coatings sintered for longer periods (up to 10 mins in this study). This change with longer plasma treatment times was associated with rutile grain growth and a decrease in surface roughness, possibly due to a densification of the mesoporous structure. The effect of TiO2 coating plasma treatment times on the conversion efficiency of the dye sensitised electrodes was also evaluated. Plasma treatments of 5 mins were found to yield the highest conversion efficiency of 6.4%.     

Hydrothermal synthesis of one-dimensional single-crystalline rutile TiO2 nanostructures and their application in dye-sensitized solar cells

One-dimensional (1D) TiO2 nanowire arrays are fabricated on transparent conducting substrates via a low temperature hydrothermal route for application in dye-sensitized solar cells (DSSCs). The as-prepared sample on fluorine-doped tin oxide (FTO) substrate is found to be single-crystalline rutile TiO2 structures from X-ray and electron diffractions. The length and diameter of the nanowires depend mainly on the growth time and temperature. With increasing the reaction time, the growth rate becomes slower and the interface adhesion between the growth nanowires and the substrate becomes weaker. In the same time the adjacent nanowires aggregate to larger the apparent diameter of the nanowire making the gaps among the nanowires to disappear at last. The nanowires exhibit flower-like morphology on the non-conducting surface of FTO substrate. By using TiO2 nanowire arrays with 2 microm long on FTO substrate as the photoanode in DSSCs, an overall light conversion efficiency of 1.58% is achieved with an open circuit voltage of 0.714 V, a short circuit current density of 4.68 mA cm(-2), and a fill factor of 0.472.     

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.     

The fabrication of CNTs/TiO(2) photoanodes for sensitive determination of organic compounds

Titanium dioxide (TiO(2)) and carbon nanotubes (CNTs) are the two most popular functional materials in recent years. In this study, CNTs/TiO(2) composite and TiO(2) photoanodes were fabricated by a dip-coating technique, followed by subsequent calcination. The resultant photoanodes were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), and UV-visible spectroscopy (UV-vis). The results suggest that the carbon nanotubes were successfully incorporated with the TiO(2) nanoparticulates without damage and that the resultant TiO(2) nanoparticles consisted of anatase and rutile. The CNTs/TiO(2) photoanodes were capable of oxidizing various types of organic compounds (e.g.?glucose, potassium hydrogen phthalate, and phenol) in aqueous solutions in a photoelectrochemical bulk cell. In comparison with the pure TiO(2) photoanode, the sensitivity of the photoanode for the detection of organic compounds has been improved by 64%, while the background current was reduced by 80% due to the introduction of the CNTs. These advantages can be ascribed to the improved adsorptivity to organic compounds, increased absorption of UV light and enhanced electron transport at the CNTs/TiO(2) photoanode due to the introduction of the CNTs.     

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。     

二氧化钛纳米晶的光催化活性研究

以苯酚的光催化降解为模型反应,研究了锐钛矿相和金红石相二氧化钛纳米晶（７￣４０ｎｍ）的光催化活性。与市售的氧化钛相比,两种晶相的纳米氧化钛均有很高的光催化活性,锐钛矿相氧化钛对苯酚的深度矿化有更高的选择性。ＴｉＯ２吸附的水及羟基会降低氧化钛的光催化活性。由于粒径减小使氧化钛的吸收带边界蓝移,粒径小的氧化钛有更高的催化活性,粒径〈１５ｎｍ时,显示出量子尺寸效应。     

Initial formation behaviour of polypyrrole on single crystal TiO2 through photo-electrochemical reaction

Hybrid materials of the organic and inorganic semiconductors have a potential to show the better performance in the charge separation at the junction upon the photovoltaic action by the presence of the space charge layer in the inorganic semiconductor. In this study, the photo-anodic polymerization was selected as a fabrication method for the hybrid materials composed of TiO2 and polypyrrole on the basis of some advantages of this method. For the process control of the photo-anodic polymerization, it is important to elucidate the formation and growth mechanisms of the organic polymer. In this study, a flat sheet of single-crystal TiO2 was used as a well-defined surface for preparation of the organic polymer of pyrrole. Photo-anodic polarization behaviour was clarified and polypyrrole was prepared on TiO2. The formation process, especially the initial step was revealed by observation of polypyrrole with atomic force microscope (AFM) and statistical interpretation of the morphology of polypyrrole in the nano-scopic level. The formation process of polypyrrole on the TiO2 surface was summarized; (1) adsorption of precursors, (2) localized formation and growth of polypyrrole under the photo-illumination, and (3) homogenous growth of polypyrrole with the external current application under the photo-illumination.     

Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites

The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO(2) nanoparticles having an average particle size of 14.4?nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO(2)-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO(2) nanoparticles serve two purposes, namely to prevent the TiO(2) nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO(2)-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO(2)-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.     

Effect of Flame Conditions on Crystalline Structure of TiO2 in Liquid Flame Spraying

Nanostructured TiO2 is a most promising functional ceramic owing to its potential utilization in photocatalytical, optical and electrical applications. Nanostructured TiO2 coating was deposited through thermal spraying with liquid feedstock. Two types of crystalline structures were present in the synthesized TiO2 coating including anatase phase and rutile phase.The effect of spray flame conditions on the crystalline structure was investigated in order to control the crystalline structure of the coating. The results showed that spray distance, flame power and precursor concentration in the liquid feedstock significantly influenced phase constitutions and grain size in the coating. Anatase phase was formed at spray distance from 150 to 250mm, while rutile phase was evidently observed in the coating deposited at 100 mm. The results suggested that anatase phase was firstly formed in the coating, and rutile phase resulted from the transformation of the deposited anatase phase. The phase transformation from anatase to rutile occurred through the annealing effect of spraying flame. The control of the phase formation can be realized through flame condition and spray distance.     

Template-free formation of vertically oriented TiO2 nanorods with uniform distribution for organics-sensing application

High-density arrays of vertically oriented TiO(2) nanorods with uniform distribution on Ti foil have been formed through template-free oxidation of Ti in hydrogen peroxide solutions. Subsequent thermal treatment was applied for growing mixed crystal structures to pursue higher performance. Morphology characterization using field emission scanning electron microscopy (FESEM) shows a nanorod diameter in the range of 20-50 nm with a length of 1.5 μm. X-ray diffraction (XRD) measurement demonstrates the crystallization of the TiO(2) nanorods prior to thermal treatment and the formation of anatase and rutile mixed phase after thermal treatment. The mixed crystal TiO(2) nanorods show a much higher performance than pure anatase in photoelectrochemical experiments. Steady-state photocurrent resulted from photocatalytic oxidation of organic compounds by TiO(2) nanorods is employed as response signal in determination of the organics to yield a linear range of 0-1.1mM for glucose. For other organics, an excellent linear relationship between the net steady-state photocurrent and the concentration of electrons transferred in exhaustive oxidation for these organics is obtained, which empowers the mixed crystal TiO(2) nanorods to serve as versatile material in organics-sensing application.     

Effects of TiO2 structures in dye-sensitized solar cell

In this work, the effects of crystalline structure of the TiO2, which is incorporated in fabrication of the n-type electrode, on the DSSC performance were investigated in terms of the energy conversion efficiency. In this effort, TiO2 nanoparticle pastes with varying contents of rutile and anatase structures were prepared by using the ethanol mixing method. The most efficient photo-electro-chemical performance was achieved for the DSSC fabricated with the TiO2 paste in which the anatase form of the nanocrystal extends to 90%.     

TiO2包覆石墨颗粒的制备及表征

以钛酸四丁酯，二乙醇胺，无水乙醇和水为主要原料，采用溶胶－凝胶技术在石墨颗粒表面包覆了TiO2，研究了复合颗粒制备的条件，表面形貌和特性，获得了金红石相TiO2完全包覆石墨的复合颗粒。     

Investigation on the sonocatalytic degradation of parathion in the presence of nanometer rutile titanium dioxide (TiO2) catalyst

The nanometer rutile titanium dioxide (TiO2) powder was adopted to act as the sonocatalyst after treatment of high-temperature activation and the ultrasound of low power was used as an irradiation source to induce heat-treated TiO2 powder performing sonocatalytic degradation of parathion. Although there are many factors influencing sonocatalytic degradation of parathion, the experimental results demonstrate that the optimal degradation condition of parathion can be obtained when the experimental conditions such as initial concentration of 50 mg/L parathion, addition amount of 1000 mg/L nanometer rutile TiO2, ultrasonic of 30-50 kHz frequency and 50 W output power, acidity of pH 10.0 and temperature of 20 degrees C are adopted. The degradation ratio of parathion surpassed 90% within 120 min ultrasonic irradiation in these optimal experiment conditions. The total degradation process of parathion has been monitored by UV-vis spectra and ion chromatography. At last, the parathions in aqueous solution are completely degraded and become some simple inorganic ions such as NO3(-), PO4(3-), SO4(2-), etc. In addition, the sonocatalytic activities of reused TiO2 catalysts were also studied and found to decline gradually along with the reused times. In this paper, the research on sonocatalytic degradation kinetics was also been performed and found to follow pseudo first-order reaction. All experiments indicated that the sonocatalytic method in the presence of nanometer rutile TiO2 powder was an advisable choice for the treatments of non- or low-transparent organic wastewaters in future.