The preparation and characterization of photocatalytically active TiO2 thin films and nanoparticles using Successive-Ionic-Layer-Adsorption-and-Reaction

Photocatalytically active TiO₂ thin-films were deposited on silicon wafers using the Successive-Ionic-Layer-Adsorption-and-Reaction technique and subsequent hydrothermal and/or furnace annealing. Atomic-force-microscopy images and X-ray diffraction measurements of the TiO₂ films obtained under various annealing conditions show how changes of the micro-scale surface structure depend on the post-SILAR treatment. The hydrogen evolution over various TiO₂ films was measured. Hydrothermally treated TiO₂ films show a higher photocatalytic activity and a much better mechanical stability compared to furnace-annealed films. The optical transmittance of TiO₂ thin films on glass substrates was also studied. A red shift was observed with increasing film thickness. TiO₂ nanoparticles (∼10 nm) that were peeled off from the TiO₂ films were investigated using high-resolution-transmission-electron-microscopy.     

One step room temperature photodeposition of Cu/TiO2 composite films and its conversion to CuO/TiO2

Cu/TiO₂ composite films were prepared at low temperature on glass substrates by a photodeposition method. Films were deposited by irradiating the substrate while in contact with an aqueous TiO₂ suspension containing copper(II) nitrate and ethanol. Cu/TiO₂ composite films of 500 nm in thickness were deposited at room temperature after a short irradiation time (15 min) with a 125 W mercury vapour lamp. According to scanning electron microscopy observations, the obtained films were homogeneous and porous. Energy dispersive X-ray spectroscopy analysis revealed a 3:1 Cu:Ti atomic ratio. Grazing angle X-ray diffraction analysis showed that the films contained Cu and TiO₂ as major components and Cu₂O as a minor component. Heat treatment at 400 °C in air for a period of 3 h transformed the initial material into a CuO/TiO₂ composite, improved the adhesion to the substrate and favoured a more regular distribution of copper oxide according to backscattering micrographs.     

真空钙热还原法制备金属钛粉的研究

在真空炉中(30~40 Pa)1273 K下,将物料放入螺纹密封的石墨坩埚中进行不同时间下的还原反应。本文采用热力学分析及X射线衍射、扫描电子显微镜及能量弥散X射线谱等方法与手段,系统研究了金属钙(Ca)与反应器中的氧气(O2)、氮气(N2)、二氧化钛(TiO2)的反应和还原时间及还原产物的预处理对得到金属钛粉(Ti)的影响。通过热力学研究,在温度低于钙的熔点(1115 K)时,密封容器内的O2与Ca的反应及N2与Ca的反应满足反应发生的热力学条件。当温度达到1273K时,Ca的饱和蒸气压p*≈p系,有利于整个气固反应进行。实验研究表明,在还原反应发生前,反应器内的O2,N2与Ca反应完全。将在1273 K下还原时间为4 h得到的还原产物在酸洗前真空挥发处理还原产物表面大量的Ca时,金属单质Ti再次被氧化成低价氧化物,最终得不到金属Ti粉。将反应时间延长至6 h时,酸洗过滤后得到形状不规则、纯度达到98.64%的Ti粉。     

Photocatalysis and characterization of the gel-derived TiO2 and P-TiO2 transparent thin films

The gel-derived TiO₂ and P-TiO₂ transparent films coated on fused-SiO₂ substrates were prepared using a spin-coating technique. Effects of phosphorus dopants and calcination temperature on crystal structure, crystallite size, microstructure, light transmittance and photocatalytic activity of the films were investigated. By introducing P atoms to Ti-O framework, the growth of anatase crystallites was hindered and the crystal structure of anatase-TiO₂ could withstand temperature up to 900 °C. The photocatalytic activities of the prepared films were characterized using the characteristic time constant (τ) for the photocatalytic reaction. The titania film with a smaller τ value possesses a higher photocatalytic ability. After exposing to 365-nm UV light for 12 h, the P-TiO₂ films calcined between 600 °C and 900 °C can photocatalytically decomposed ≥ 84 mol% of the methylene blue in water with corresponding τ ≤ 7.1 h, which were better than the pure TiO₂ films prepared at the same calcination temperature.     

Preparation, characterization and application of TiO2 nanoparticles surface-modified by DDAT

DDAT(S-1-Dodecyl-S′-(α, α′-dimethyl-α″-acetic acid) trithiocarbonate) modified TiO₂ photocatalysts were prepared by hydrothermal treatment before TiO₂ crystallization. The adsorption of DDAT onto the surface of titania nanoparticles led the shifting of the onset wavelength of the optical absorption in the visible range corresponding to ligand-to-metal charge transfer transition within the surface-modified complex. The interaction of TiO₂ nanoparticles with DDAT was investigated by infrared spectra. The XRD indicated that the modification process could not influence the crystallite phase of TiO₂. The photocatalytic studies suggested that the DDAT modified TiO₂ photocatalysts showed enhanced photocatalytic efficiency of photodegradation of 2,4-dichlorophenol compared with the as-prepared TiO₂ under visible-light irradiation.     

Photoactive and self-cleaning TiO2-SiO2 thin films on 316L stainless steel

In this study, TiO₂-SiO₂ nanocomposite films with different amounts of SiO₂ were prepared by sol-gel process and were coated onto stainless steel 316L. The effect of addition of various amount of SiO₂ in the precursor solution on the photocatalysis, photo-generated hydrophilicity and self-cleaning property of TiO₂ thin films was investigated by X-ray diffraction, Fourier transform infrared spectroscopy, water contact angle measurements and UV spectroscopy. In the tested ranges of SiO₂ content and sintering temperature, the highest photocatalytic activity and self-cleaning property were observed in the 15 mol% SiO₂ sample sintered at 750 °C. Addition of less than 30 mol% SiO₂ had a suppressive effect on the transformation of anatase to rutile and on the crystal growth of anatase in the sintering heat treatment. Phase separation occurred in the composite films for SiO₂ content of 30 mol% or more.     

低温等离子体射流制备二氧化钛薄膜及其光催化活性的研究

利用大气压低温等离子体射流技术,以空气为放电气体,四氯化钛为钛源,在玻璃载玻片基底上制备了二氧化钛薄膜。利用扫描电镜及椭圆偏振仪分析测量了薄膜的表面形貌与沉积速率。利用紫外光照射硬脂酸分解速率评价所制备薄膜的光催化活性,结果显示在同一放电输入功率及气体流量条件下,四氯化钛前驱体引入位置距射流枪枪口越近,所制备的二氧化钛薄膜光催化性能越高。在同一反应位置时,放电输入功率的增加有助于提高二氧化钛薄膜的光催化活性。     

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.     

Effect of SnO2 on the photocatalytical properties of TiO2 films

TiO₂/SnO₂ thin films with different tin atomic percentages were successfully prepared on glass substrates by the spray pyrolysis method from an alcoholic solution of TiO[C₅H₇O₂]₂ with different concentrations of SnCl₄. The TiO₂/SnO₂ thin films prepared at 450 °C presented the anatase phase in polycrystalline configuration from %Sn = 0 in the starting solution up to %Sn = 20, at higher tin content the films present an amorphous configuration. The resulting thin films have a homogeneous surface structure with some porosity. The photocatalytical properties of the films were evaluated with the degradation of methylene blue. The products of the degradation reaction were identified by ¹H nuclear magnetic resonance and the film properties were studied by atomic force microscopy, scanning electron microscopy, UV–Vis spectroscopy, and X-ray diffraction.     

Microstructure and optical properties of photoactive TiO2:N thin films

In this work, we have chosen oxidation of TiN thin films as a feasible method for preparation of nitrogen-doped titanium dioxide thin films, TiO₂:N, for photocatalytic applications. DC reactive magnetron sputtering with the plasma emission control was used for deposition of stoichiometric TiN thin films. The microstructure and chemical composition of films before and after oxidation were investigated by means of RBS, X-ray diffraction (XRD) in grazing incidence diffraction (GID) configuration, AFM and XPS techniques. The electrical conductivity was measured by the van der Pauw method as a function of the oxidation temperature. The optical transmittance and reflectance spectra of the films were measured over the visible and UV ranges of the light spectrum. GID diffraction patterns of as-sputtered TiN thin films and those after oxidation indicate that TiO₂ rutile is formed at around 300 °C. Nitrogen is still present as indicated by XPS studies even when XRD detects the rutile only. Optical absorption of thin films oxidized at 450 °C is shifted towards the visible range of the light spectrum.     

Enhanced photocatalytic activity of TiO2-incorporated nanofiber membrane by oxygen plasma treatment

In this paper, we report on the high-performance photocatalysis of polymeric TiO₂ membranes modified by oxygen plasma treatment for water purification. TiO₂-nanopowder-incorporated poly ε-caprolactone (PCL/TiO₂; PT) nanofibers were prepared by electrospinning at various concentrations of TiO₂ (1, 3, 5, and 7 wt.%) and then treated by atmospheric plasma with oxygen gas (OAP). As the TiO₂ content increased, the surface roughness and photocatalytic efficiency of the nanofibers increased. The tensile strength of the membranes increased until the TiO₂ content reached 3 wt.% but led to a degradation of the mechanical property at higher concentrations owing to significant agglomeration of TiO₂. The hydrophilicity of OAP membranes increased as the TiO₂ nanopowders were exposed and the production of polar species was induced at the surface of the PT nanofibers. The OAP-PT membranes were observed to enhance the degradation of harmful organics. The results indicate that OAP-PT membranes are useful photocatalysts for purifying water.     

Photodegradation of clopyralid in TiO2 suspensions: Identification of intermediates and reaction pathways

The work is concerned with the kinetics, identification of intermediates and reaction pathways of the photocatalytic degradation of the herbicide clopyralid (3,6-dichloropyridine-2-carboxylic acid) in UV illuminated aqueous suspensions of TiO₂ (Degussa P25). In the investigated concentration range (0.5–3.0 mM) the photocatalytic degradation kinetics of clopyralid in the first stage of the reaction follows approximately a pseudo-first kinetic order. The highest reaction rate was observed at 4 mg mL⁻¹of catalyst concentration, the apparent activation energy of the reaction being 7.74 kJ mol⁻¹. The effect of the presence of hydrogen peroxide, potassium bromate, and ammonium persulfate, acting as electron acceptors along with molecular oxygen, were also studied. By studying the effect of ethanol as a hydroxyl radical scavenger it was shown that the heterogeneous catalysis takes place mainly via hydroxyl radicals. The reaction intermediates (3,6-dichloropyridin-2-ol, 3,6-dichloro hydroxypyridine-2-carboxylic acid, and 3,3′,6,6′-tetrachloro-2,4′-bipyridine-2′-carboxylic acid) were identified and the kinetics of their appearance/disappearance was followed by LC–MS/MS (ESI+). Tentative photodegradation pathways were proposed and discussed.     

Synthesis of carbon-doped TiO2 nanoparticles using CO2 decomposition by thermal plasma

This study examined the synthesis of carbon-doped titanium dioxide using TiCl₄ and CO₂ as titanium and carbon sources, respectively, by thermal plasma at atmospheric pressure. The effect of the CO₂ gas flow rate on the preparation of TiO₂ was investigated. The results showed that the decomposition rate of CO₂ was 90% at a CO₂ gas flow rate of 1 L/min. When TiCl₄ was added to produce TiO₂, the decomposition rate of CO₂ reached 95% at a CO₂ gas flow rate of 1 L/min. The resulting powders contained mixed anatase and rutile phases with particle sizes ranging from 20 to 50 nm. The carbon in the CO₂ acted as a dopant to produce the carbon-doped TiO₂. The prepared samples were mainly characterized by X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area measurements and ultraviolet-visible spectroscopy.     

Deposition of photocatalytic TiO2 layers by pulse magnetron sputtering and by plasma-activated evaporation

Crystalline TiO₂ thin films, especially layers with predominantly anatase phase, exhibit photocatalytic activities resulting in photoinduced hydrophilic, self-cleaning and antifogging properties. In this paper, a comparison of the photocatalytic properties of layers deposited with two different PVD techniques is given.On one hand, a reactive pulse magnetron sputtering (PMS) system has been used to obtain TiO₂ films at dynamic deposition rates from 8 to 50 nm m/min. On the other hand, TiO₂ layers were deposited by reactive electron beam evaporation at very high deposition rates between 500 and 1000 nm m/min. An additional spotless arc discharge (Spotless arc Activated Deposition—SAD process) was used for plasma activation to improve layer properties. Photoinduced hydrophilicity was investigated by measuring the decrease of the water contact angle during UV-A irradiation.     

Conductivity of nanometer TiO2 thin films by magnetron sputtering

The conductivity of nanometer TiO₂ thin films was presented in this paper. The dependence of the conductivity of TiO₂ thin films on the thickness of the film and the substrate material were educed. The TiO₂ films were deposited by reactive magnetron sputtering of a Ti targets in an Ar+O₂ mixture in a conventional sputtering reactor. The thickness of the films deposited on Ti varied in the range from 15 to 225 nm. The resistivity of the films was measured at room temperature in the air. It was found that the conductivity of TiO₂ thin films varies in the range from conductor, semiconductor to nonconductor. This was attributed to electrons transfer at the interface between the TiO₂ and substrates, and the depth of electrons transfer was determined by the difference of work function.     

Silver loaded WO3 − x/TiO2 composite multifunctional thin films

Multifunctional WO_3 − x-TiO₂ composite thin films have been prepared by sol-gel synthesis and shown to be good visible light photocatalysts whilst retaining a desirable underlying blue colouration. The WO_3 − x-TiO₂ composite thin films were further enhanced using silver nanoparticles synthesised in-situ on the surface from the photo-degradation of silver nitrate solution. Thin films were characterised using X-ray diffraction, Raman, Scanning electron microscopy and UV-visible spectroscopy and shown to photo degrade stearic acid, using white light λ = 420-800 nm.     

Photoreduction of CO2 by TiO2 nanocomposites synthesized through reactive direct current magnetron sputter deposition

The photoreduction of CO₂ into methane provides a carbon-neutral energy alternative to fossil fuels, but its feasibility requires improvements in the photo-efficiency of materials tailored to this reaction. We hypothesize that mixed phase TiO₂ nano-materials with high interfacial densities are extremely active photocatalysts well suited to solar fuel production by reducing CO₂ to methane and shifting to visible light response. Mixed phase TiO₂ films were synthesized by direct current (DC) magnetron sputtering and characterized by X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM) and transmission electron microscope (TEM). Bundles of anatase-rutile nano-columns having high densities of two kinds of interfaces (those among the bundles and those between the columns) are fabricated. Films sputtered at a low deposition angle showed the highest methane yield, compared to TiO₂ fabricated under other sputtering conditions and commercial standard Degussa P25 under UV irradiation. The yield of methane could be significantly increased (~ 12% CO₂ conversion) by increasing the CO₂ to water ratio and temperature (< 100 °C) as a combined effect. These films also displayed a light response strongly shifted into the visible range. This is explained by the creation of non-stoichiometric titania films having unique features that we can potentially tailor to the solar energy applications.     

TiO2 thin films for dyes photodegradation

The aim of the present study is to investigate the influence of the TiO₂ specific surface (powder, film) on the photocatalytic degradation of methyl orange. Porous TiO₂ films were deposited on transparent conducting oxide substrates by spray pyrolysis deposition. The films were characterized by X-ray diffraction (XRD), Scanning Electronic Microscopy, and the UV-Vis spectroscopy. The XRD spectra of nanoporous TiO₂ films revealed an anatase, crystalline structure that is known as the most suitable structure in photocatalysis. The average thickness of the films was 260 nm and the measured band gap is 3.44 eV. The influence of the operational parameters (dye concentration, contact time) on the degradation rate of the dye on TiO₂ was examined. There were calculated the kinetic parameters and the process efficiency. Using thin films of TiO₂ is technologically recommended but raises problems due to lowering the amount of catalyst available for the dye degradation.     

Photocatalytic characteristics of TiO2 nanotubes with different microstructures prepared under different pulse anodizations

In this work, different positive voltages of a pulsed waveform, time intervals and electrolyte stirring were used to prepare by anodization of pure titanium plates, a series of TiO₂ thin films based on nanotubes with different morphologies and dimensions. Electrolyte stirring results in large size TiO₂ nanotubes with uneven surface morphology and less oriented directions. The titanium plates containing the TiO₂ thin films were further annealed at 450 °C for 30 min under air. It was found that only crystalline anatase was formed under this condition. Both methylene blue degradation and antibacterial tests against Escherichia coli were performed to evaluate the photocatalytic performance of these TiO₂ films. Better methylene blue degradation ability was achieved by TiO₂ nanotubes prepared under electrolyte stirring. However, the antibacterial ability of the annealed TiO₂ nanotubes was affected by their inner diameter rather than their length. It is also concluded that the anodized TiO₂ nanotube arrays fabricated in this work are promising for photo-induced methylene blue degradation and bacteria killing applications.     

Thermal optical properties of TiO2 films

A fibre optic experimental arrangement was used to determine the thermo-optic coefficient (dn/dT) of electron beam deposited titanium dioxide coatings on the cleaved end faces of multimode optical fibres for a wavelength range between 600 and 1050 nm. The temperature-induced change in the index of refraction (n) and extinction coefficient (k) were successfully determined from reflection spectra. Measurements of n and k at various wavelengths for different temperatures enabled the determination of dn/dT and dk/dT. It was found that dn/dT takes different values at different temperature ranges. For example, at 800 nm, dn/dT was (−1.77±0.7)×10⁻⁴ K⁻¹, between 18°C and 120°C, and took a value of (−3.04±0.7)×10⁻⁴ K⁻¹ between 220°C and 325°C.