Ultrafast nonresonant response of TiO2 nanostructured films

We present a detailed study of the nonresonant third-order ultrafast response of TiO(2) nanostructured films, combining a classical heterodyned optical Kerr effect experiment, with two polarization selective Kerr techniques, based on transient lensing and phase modulation effects. The complementarity of these techniques is highlighted and demonstrated with calculations. Different aspects of the experimental results are addressed in detail and, finally, the possibilities of performing experiments on liquid dynamics in the pores of TiO(2) films, are discussed in the light of the present results.     

Photoinduced hydrophilicity of heteroepitaxially grown ZnO thin films

Single crystalline ZnO thin films were heteroepitaxially grown on sapphire substrates by rf-magnetron sputtering. The ZnO films on sapphire A and C face were oriented along the (0001) direction, whereas the ZnO film on sapphire R face was oriented along the (11-20) direction. The rate of photoinduced hydrophilic conversion strongly depended on the surface crystal structure. The ZnO film oriented along the (11-20) direction exhibited a higher hydrophilicizing rate than those oriented along the (0001) direction. The high hydrophilicizing rate of the ZnO oriented along the (11-20) direction is due to its surface atomic arrangement. The outermost layer of the ZnO surface of the (11-20) face contains oxygen ions, which are considered to be energetically reactive sites and responsible for the hydrophilic conversion.     

Modification of photocatalytic TiO2 thin films by electron beam irradiation

Noble metal-modified TiO₂ films were prepared by electron beam deposition of Pt, Pd, Au and Ag on the surface of TiO₂ films with diameters ranging from <1 nm to 500 nm. The morphology of the films was characterized by X-ray diffractometry (XRD), field emission scanning electron microscope (FMSEM) and transmission electron microscope (TEM). The photocatalytic capability of the films were tested and compared by degradation of methyl orange (MO) in aqueous solutions under both UV and visible light illumination.     

Nitrogen-doped TiO2 thin films: photocatalytic applications for healthcare environments

N-doped TiO(2) has for many years received interest as visible light photocatalytic materials. Here we give our perspective on the subject with special consideration towards the use of visible light photocatalysts in the field of antimicrobial materials with applications in healthcare environments. The subject is reviewed and critiqued from synthetic techniques to characterisation and assessment of functional properties. N-doped TiO(2) has huge potential to form commercially viable antimicrobial surfaces that are easily implemented within the healthcare environment. We aim to shed light on the illusive nature of the mechanism of the different types of N-doping and comment on how these affect the properties of the catalysts themselves. Small concentrations of nitrogen doped under mild conditions lead to interstitial doping, which also promotes the creation of oxygen vacancies. Many believe that it is these oxygen vacancies that actually promote the formation of visible light photocatalysis and hence there is an indirect correlation between the interstitial doping and the photocatalysis. As the concentration of interstitial nitrogen increases the oxygen vacancies increase, however the presence of oxygen vacancies in turn encourages substitutional doping which then fills the oxygen vacancies. This cyclic relationship leads to photocatalysts that are very sensitive to changing nitrogen concentration.     

Preparation and photoactivity of nanostructured anatase, rutile and brookite TiO2 thin films

Photoactive films consisting of pure anatase, brookite or rutile TiO2 were prepared by dip coating from water dispersions obtained by using TiCl4 as the precursor under similar mild experimental conditions.     

Synthesis and photocatalytic properties of highly crystalline and ordered mesoporous TiO2 thin films

Highly crystalline and ordered mesoporous TiO2 thin films have been synthesized by stabilization of the mesostructure with confined carbon; the films exhibit 2.5% photoconversion efficiency for the water photolysis at zero-bias and Xe lamp illumination of 40 mW cm(-2).     

Atomic layer deposition of TiO2−xNx thin films for photocatalytic applications

Titanium dioxide (TiO₂) is recognized as the most efficient photocatalytic material, but due to its large band gap energy it can only be excited by UV irradiation. Doping TiO₂ with nitrogen is a promising modification method for the utilization of visible light in photocatalysis. In this work, nitrogen-doped TiO₂ films were grown by atomic layer deposition (ALD) using TiCl₄, NH₃ and water as precursors. All growth experiments were done at 500 °C. The films were characterized by XRD, XPS, SEM and UV–vis spectrometry. The influence of nitrogen doping on the photocatalytic activity of the films in the UV and visible light was evaluated by the degradation of a thin layer of stearic acid and by linear sweep voltammetry. Light-induced superhydrophilicity of the films was also studied. It was found that the films could be excited by visible light, but they also suffered from increased recombination.     

TEM evidence of ultrastructural alteration on Pseudomonas aeruginosa by photocatalytic TiO2 thin films

The antibacterial efficiency of longwave UV-irradiated TiO(2) thin films as well as the ultrastructural damage on bacterial cells was evaluated using Pseudomonas aeruginosa as a model. The quantitative antibacterial efficiency assays showed a bacterial inhibition in the range of 32-72% at different times of irradiation. Transmission electron microscopy (TEM) was used to detect the effect of irradiation of TiO(2) thin films on the ultrastructure of the bacterial cell in order to reveal possible cellular damage. After 40 min irradiation, an abnormal cellular division was observed: instead of a normal septum, an 'elongated bridge' was formed. At a longer irradiation time, wavy structures all around the outer cell membrane were observed, and also some bubble-like protuberances, which expelled inner material. The mechanism of irreversible bacterial cell damage caused by the photocatalytic effect of TiO(2) could be related to abnormal cell division, aside from the reported physicochemical alteration of the cell membrane.     

Photoinduced charge property of Ag‐TiO2 films and its relationships with photocatalytic activity under visible illumination

In this article, TiO₂ films were synthesized by traditional spin coating method. To improve their photocatalytic activities, we deposited silver on these films by photodeposition. These films also were characterized by several testing techniques, such as X‐ray diffraction, ultraviolet–visible diffuse reflection spectrum, XPS, Raman spectroscopy (Raman), surface photovoltage spectroscopy, and SEM. The activity of different films was evaluated for degrading rhodamine B solution under visible illumination. The effects of AgNO₃ solution concentration on photoinduced charge property and photocatalytic activity were investigated. The results show that the Ag‐TiO₂ film immersed in 10^?3 mol·L^?1 AgNO₃ solution exhibits higher activity, which is in good agreement with the characterization results. The weaker the surface photovoltage spectroscopy signal, the higher the photocatalytic activity. Moreover, the activity of some films is higher than that of international Degussa P‐25 TiO₂ under visible illumination. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced photo-catalytic activity of TiO2 nanostructured thin films under solar light by Sn and Nb co-doping

In this study, preparation of Sn and Nb co-doped TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of co-doping content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), field emission SEM (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy (XPS). XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania Rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The prepared co-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue (MB) solution under solar irradiation. Comparison with undoped and Sn or Nb-doped TiO₂, codoped TiO₂ shows an obviously higher catalytic activity under solar irradiation.     

Effect of HF treatment on the activity of TiO2 thin films for photocatalytic water splitting

The effects of HF treatment on the activity of TiO₂ thin films for the photocatalytic water splitting reaction have been investigated. TiO₂ thin films treated with HF solution (HF-TiO₂) were found to exhibit a remarkable enhancement of the photocatalytic activity for H₂ evolution from a methanol aqueous solution, as well as efficient photoelectrochemical performance under UV light irradiation as compared with the untreated TiO₂. Moreover, Pt-loaded HF-TiO₂ thin films were found to act as efficient and stable photocatalysts for the decomposition of water under UV light irradiation. The mechanistic insights obtained in the present study will be useful in the design of highly efficient photocatalysts for the decomposition of water.     

Double-layered TiO2-SiO2 nanostructured films with self-cleaning and antireflective properties

Dual function of self-cleaning and antireflection can be created in double-layered TiO2-SiO2 nanostructured films. The film were prepared by (1) layer-by-layer deposition of multilayered SiO2 nanoparticles with polydiallyldimethylammonium (PDDA) cations, (2) layer-by-layer deposition of multilayered titanate nanosheets with polications on PDDA/SiO2 multilayer films, and (3) burning out the polymer and converting titanate nanosheets into TiO2 by hearing at 500 degrees C. The as-prepared films, consisting of a porous SiO2 bottom layer and a dense TiO2 top layer, improved the transmittance of glass or quartz substrates, as demonstrated by transmission spectra collected at normal incidence. The photocatalytic properties of the films were studied by the change of the water contact angle together with the decay of the IR absorption of the hydrocarbon chain of octadecylphosphonic-acid-modified films under 2.6 mW cm-2 UV illumination. Both the antireflective and the photocatalytic properties of the films were dependent on the number of PDDA/nanosheet bilayers deposited. however, excellent surface wettability of the films for water was obtained, independent of the preparation conditions. The experimental findings are discussed in terms of the special structure of the double-layered nanostructured film.     

Highly efficient visible-light-induced photocatalytic activity of nanostructured AgI/TiO2 photocatalyst

Nanostructured AgI/TiO(2) photocatalyst was synthesized by a feasible approach with AgNO(3), LiI, and Ti(OBu)(4) and characterized by X-ray diffraction, transmission electron microscopy, angle-dependent X-ray photoelectron spectroscopy, diffusive reflectance UV-vis spectroscopy, Raman spectroscopy, photoluminescence, and the Brunauer-Emmett-Teller technique. The results of characterization reveal that the nanostructured AgI/TiO(2) has a novel core/shell/shell nanostructure of AgI/Ag-I(2)/TiO(2). Compared with TiO(2) (P25) supported AgI, the formation of the nanostructure results in substantial shifting of the absorption edge of AgI to red, enhancement of the absorption intensity, and the appearance of a strong tail absorption above 490 nm, which is assigned to the absorption of I(2) and Ag. Photocatalytic tests show that the nanostructured AgI/TiO(2) photocatalyst exhibited very high visible-light-induced photocatalytic activity for the photodegradation of crystal violet and 4-chlorophenol, which is 4 and 6 times higher than that of P25 titania supported AgI, respectively. The highly efficient visible-light-induced photocatalytic activity of the nanostructured AgI/TiO(2) is attributed to its strong absorption in the visible region and low recombination rate of the electron-hole pair due to the synergetic effect among the components of AgI, Ag, I(20, and TiO(2) in the nanostructured AgI/TiO(2).     

The effect of Sn dopant on crystal structure and photocatalytic behavior of nanostructured titania thin films

In this study, preparation of Sn doped (0–30 mol % Sn) TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of Sn content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), field emission SEM (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). Surface topography and surface chemical state of thin films were examined by atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). XRD patterns showed an increase in peak intensities of the rutile crystalline phase by increasing the Sn dopant. The prepared Sn-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue solution under UV irradiation. The result shows that doping an appropriate amount of Sn can effectively improve the photo-catalytic activity of TiO₂ thin films, and the optimum dopant amount is found to be 15 mol%. The Sn⁴⁺ dopants substituted Ti⁴⁺ in the lattice of TiO₂ and increased surface oxygen vacancies and the surface hydroxyl groups. TEM results showed small increase in planar spacing (was detected by HR-TEM caused by Sn dopants in titania based crystals).     

钼掺杂二氧化钛复合膜的光催化及光电性质

二氧化钛光催化反应在光电转换、光化学合成、光催化降解环境污染物及自清洁材料的制备等方面具有广阔的应用前景。但二氧化钛只有在波长小于378砌的紫外光的激发下,价带电子才能跃迁到导带上,形成光生电子与空穴的分离,对太阳能的利用率不高。     

Photocatalysis and hydrophilicity of doped TiO2 thin films

TiO(2) thin films were prepared using the dip-coating method with a polymeric sol including additives such as Al, W, and Al+W to examine two major properties: photocatalysis and hydrophilicity. W-doped films showed the best photocatalytic efficiency, while Al-doped film was poorer than undoped samples. However, good hydrophilicity in terms of saturation contact angle and surface conversion rate was found in Al- and (Al+W)-mixed-doped films. It was found that deep electron-hole traps and high surface acidity of W-doped TiO(2) thin film were the major factors in high photocatalytic efficiency. In addition, low surface acidities of Al- and (Al+W)-doped films provided better hydrophilicity than W-doped ones. However, the amount of [Ti(3+)] point defects on the surface was another major factor, probably the most important, in getting the best hydrophilicity. Conclusively, it seemed that many parts of the photocatalysis mechanism depend more on bulk-related properties than do those of hydrophilicity, which can be defined as an interfacial (surface) or near-surface-restricted process.     

Electrochromic properties of sputtered TiO2 thin films

TiO₂ thin films were deposited on ITO/Glass substrates by the rf magnetron sputtering in this study. The electrochromic properties of TiO₂ films were investigated using cyclic voltammograms (CV), which were carried out on TiO₂ films immersed in an electrolyte of 1 M LiClO₄ in propylene carbonate (PC). As- deposited TiO₂ thin film was amorphous, while the films post-annealed at 300~600°C contained crystallized anatase and rutile. With the increase of the annealing temperature, the surface roughness of film increased from 1.232 nm to 1.950 nm. Experimental results reveal that the processing parameters of TiO₂ thin films will influence the electrochromic properties such as transmittance, ion-storage capacity, inserted charge, optical density change, coloration efficiency and insertion coefficient.     

陶瓷泡沫空气过滤器涂覆中孔TiO2薄膜用于室内空气净化中高效光催化降解NO

由于人们80%的时间呆在室内,室内空气的质量直接影响人类健康,因此近年来室内空气质量越来越受到人们的关注.室内污染物包括CO氮氧化物(NOx)和挥发性有机化合物(VOCs),它们给人体健康带来众多负面影响.更为重要的是,考虑到节能,现代建筑的空气密闭性大都较高,但这种减少吸入新鲜空气的设计直接导致室内各种污染物的累积.有些家用电器,如燃气灶和热水器,在使用的时候会涉及到煤、油和天然气的燃烧,特别是通风较差的情况下会成为室内主要的污染源.常规的治理技术,包括吸附和过滤,其成本相对较高,也不适用于低浓度污染物的治理.尤其是更换不及时的过滤器在排风系统中可能会成为VOCs的一个来源.因此,很有必要开发一种新型的技术以降低室内污染物的浓度和保持一个清洁的室内空气环境,从而保障人们的身体健康.光催化是去除室内空气污染物的有效方法.例如, TiO2、钛酸铋和钛酸锶等具有强氧化能力和稳定的光催化活性,因而是高效的光催化剂.一般而言,通常报道的TiO2光催化剂是高度分散的、或悬浮于液体介质中的细小颗粒或粉末.然而,粉末状的TiO2光催化剂不适宜于室内空气净化,因为它变得可吸入而对人体健康造成不利的影响.因此,人们尝试将TiO2颗粒作为薄膜固定在不同的刚性载体上,如玻璃、不锈钢和铝合金板.对基体进行涂覆可显著影响光催化时反应物的表面吸附行为.一般而言,光催化薄膜通常涂覆在平面上,如蜂窝空气过滤器.三维(3D)多孔的陶瓷泡沫对气体通过具有非常好的流体性质,因此本文以它作为涂覆的基体.这种陶瓷泡沫具有3D多孔结构,多种孔密度、比表面积和化学性质.3D多孔陶瓷泡沫空气过滤器的床层空隙率较高,因此使用时压降较低,且不像蜂窝空气过滤器,它具有复杂多变的孔结构,可增强流体的扰动和混合.另外,3D多孔陶瓷泡沫空气过滤器的开发多孔和网状的结构使得在催化体系具有非常好的气体动力学性质,催化剂表面和气体反应物有充分的接触.多孔材料在液相或气相催化反应中具有独特的优势,因此,陶瓷泡沫、多孔的氧化铝、多孔硅胶.分子筛和活性炭经常被用作催化剂载体.在固体基体上TiO2膜的形成可能使得TiO2光催化剂的有效比表面积降低,从而导致其光催化活性下降.然而,由于具有中孔结构的TiO2薄膜的比表面积大,其用于催化反应的活性位也更多,因此使用时仍然具有较高的活性.前期研究表明,涂覆在平面玻璃、不锈钢和氧化铝基体上的中孔TiO2薄膜用于环境净化时表现出增强的光催化效率.另外,室内环境中NO和NO2的浓度一般分别为几百个ppb之内和100 ppb以下.可见, NO是主要的室内空气污染物,对人体健康危害较大.基于此,本文首次采用反胶束法将中孔锐钛矿TiO2薄膜均匀一地涂覆在3D多孔高比表面积的泡沫过滤器上,采用X射线衍射、扫描电镜、X射线光电子能谱、N2吸附-脱附、紫外-可见光光谱和原子力显微镜对所制样品进行了表征,并将样品用于紫外光下催化降解NO,以揭示所制的中孔TiO2涂层具有高的比表面积和高的光催化活性,从而克服使用TiO2粉末所带来的不足.结果表明,由于中孔TiO2薄膜涂层具有较大的有效比表面积,其表面存在很多吸附活性位,用于吸附在反应过程中形成的水蒸汽、气相反应物和产物,因而具有更高的光催化活性,因此在陶瓷泡沫空气净化系统中可以高效地光催化NO降解：在所考察的不同孔密度的陶瓷泡沫过滤器涂覆的TiO2上400 ppb的NO单程转化率均在92.5%以上,高于涂覆在平面陶瓷砖上的TiO2.该陶瓷过滤器的3D多孔特性可增强流体的扰动和混合,使得气相反应物与光催化剂表面有着充分的接触;其大的孔密度也导致高的光催化速率.另外,本文所制样品在所有反应过程中均保持较高且稳定的NO降解速率,这表明其在NO降解反应中没有失活.