Influence of heat treatment on the particle size of nanobrookite TiO2 thin films produced by sol-gel method

Pure nanobrookite titania (TiO₂) thin films were deposited on glass substrates by the spin-coating method using titanium butoxide and acetic acid. The particle sizes of TiO₂ films were controlled by heat treatment temperatures. The activation energy for particle growth was calculated as 23.1 kJ/mol. The structural and optical properties of the nanobrookite TiO₂ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), ultraviolet-visible absorption spectroscopy (UV-vis), and Fourier transform infrared spectroscopy (FTIR).     

Micro-arc oxidation of TC4 substrates to fabricate TiO2/YAG:Ce compound films with enhanced photocatalytic activity

This paper introduces a process for “in situ” preparing TiO₂ photocatalytic film compounded with YAG:Ce³⁺ semiconductor upon titanium alloy by using micro-arc oxidation (MAO). The surface morphology, chemical compositions, phase structures and photocatalytic properties of the films were characterized and measured by field emission gun scanning electron microscope (FEG-SEM), energy-dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electro-chemical workstation and UV-vis spectrophotometer. The results show that the YAG:Ce³⁺ semiconductor particles which were added in the electrolyte had been homogenously compounded within the TiO₂ film during MAO. Compared with the pure TiO₂ film, the compounded film exhibited much larger specific surface area, stronger absorption in the visible light and higher photo-generated current density, which improves the photocatalytic property markedly. It is expected that MAO will provide a simple, economic and promising approach for preparing a superior photocatalytic TiO₂ film.     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

Fabrication of patterned TiO2 thin film by a wet process

Hydrophobic/hydrophilic patterned TiO₂ thin film was successfully fabricated on a glass substrate by a wet process. A micro-nano complex structure with a high roughness was fabricated by a layer-by-layer selfassembly and liquid phase deposition (LPD) method. To fabricate superhydrophobic TiO₂ thin films, TiO₂ nanoparticles were deposited on the surface of (PAH/PAA) thin film by a LPD method and the surface of TiO₂ was modified by a hydrophobic treatment using fluoroalkyltrimethoxysilane. The RMS roughness and water contact angle of the prepared TiO₂ thin film were ca. 65.6 nm and ca. 155°. The superhydrophobic surface exposed to UV light changed to a hydrophilic surface by the photocatalytic property of TiO₂ to decompose a hydrophobic group. Finally, hydrophobic/hydrophilic patterned TiO₂ thin film with a 300 ??m dot size was fabricated. The surface morphology, transmittance, surface roughness and water contact angle of the prepared thin films were measured by a field emission scanning electron microscope, an atomic force microscope, a UV-Vis spectrophotometer and a contact angle meter.     

Preparation of mesoporous titania particles using ionic liquid dissolving starch as templates

A mesoporous titania photocatalyst was prepared via calcining the solution of ionic liquid (1-methyl-3-butyl imidazolium bromide, [BMIM]Br) containing tetrabutyl titanate (TBT) and starch. The microstructure of the prepared mesoporous titania was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ adsorption/desorption isotherm. The results indicate that the resulting mesoporous titania has a grain size of about 13.9 nm, a special surface area of 106 m²/g, and a pore volume of 0.22 cm³/g, and the pore size can be adjusted by the concentration of starch in ionic liquid. The photocatalytic activity of mesoporous titania in the degradation of methyl orange solution was determined. The effect of the specific surface area of mesoporous titania on the photocatalytic activity was also studied. The prepared mesoporous titania exhibits a high catalytic activity.     

Characteristics of N-doped TiO2 nanotube arrays by N2-plasma for visible light-driven photocatalysis

N-doped TiO₂ nanotube arrays were prepared by electrochemical anode oxidation of Ti foil followed by treatment with N₂-plasma and subsequent annealed under Ar atmosphere. The morphologies, composition and optical properties of N-doped TiO₂ nanotube arrays were characterized using field-emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction spectrometer (XRD), Photoluminescence (PL) and UV-vis diffusion reflection spectroscopy (UV-vis DRS). Methylene blue (MB) solution was utilized as the degradation model to evaluate the photocatalytic activity of the samples under visible light irradiation. The results suggested N₂-plasma treatment created doping of nitrogen onto the surface of photoelectrodes successfully and the N-doped TiO₂ nanotube arrays display a significantly enhancement of the photocatalytic activity comparing with the pure TiO₂ nanotube arrays under the visible light irradiation.     

阳极氧化法制备TiO2膜在模拟深海热液区的耐腐蚀性能

以恒压阳极氧化方法在钛基体上制备TiO₂氧化膜,使用水热釜模拟深海热液区的条件研究其耐腐蚀性能。采用XRD、SEM、接触角测定仪对氧化膜以及腐蚀试样产物进行晶型、表面结构、化学成分和亲疏水性能测定,使用动电位扫描方法对其进行极化曲线测试。结果表明,钛试样和阳极氧化钛试样在模拟深海环境条件下,经过腐蚀反应在表面都生成了一层非致密的TiO₂ 膜,对基体并不能起到保护作用,而阳极氧化生成的致密TiO₂ 膜对基体能够起到很好的保护作用。经腐蚀后钛试样表面有TiH₂相的形成,腐蚀电位负移0.45 V。而阳极氧化钛试样表面没有TiH₂相的形成,且腐蚀电位负移较小,表现出良好的耐腐蚀性能。     

Amphiphilic and photocatalytic behaviors of TiO2 nanotube arrays on Ti prepared via electrochemical oxidation

Amphiphilic TiO₂ nanotube arrays (TiO₂ NTs) were fabricated through electrochemical oxidation of Ti in solution containing H₃PO₄ and NaF. Scanning electron microscopic analysis shows that the as-prepared TiO₂ NTs have an average pore diameter of 100 nm and a wall thickness of 15 nm. The electrochemical oxidation of Ti can be divided into four stages. In the first stage, when the potential is very low, oxygen formation and Ti dissolution are the major reactions. The second stage corresponds to a slightly higher potential, but less than 2.5 V. In this stage, the formation of TiO₂ film occurs. When the potential is increased to the even higher range from 2.5 V to 6 V, the TiO₂ film dissolves and nanoporous surface structure is generated. This is the third stage. Further increase of the potential enters stage four. The high potentials cause the self-organization of the nanostructure and allow the formation of well-aligned TiO₂ NTs. We also found that the change in surface condition of Ti by annealing heat treatment affects the film dissolution kinetics. As compared with TiO₂ thin film, the TiO2 NTs show higher photocatalytic activity on decomposing Rhodamine B. The surface of the TiO₂ NTs can be wetted by both water and oil. Such an amphiphilic property comes from the capillary effect of the nanochannel structure of the TiO₂ NTs. Because of the amphiphilic property and the photocatalytic activity, we conclude that the TiO₂ NTs have the capability of self-cleaning.     

Fabrication and photocatalytical properties of flower-like TiO2 nanostructures

Three-dimensional(3D)flower-like anatase TiO2 nanostructures and flower-like titanate nanostructures were successfully synthesized via hydrothermal synthesis followed by post-treatment from titanium powder.The flower-like anatase TiO2 nanostructures were characterized in detail with scanning electron microscopy(SEM),X-ray diffraction(XRD),UV-vis spectrum and nitrogen adsorption-desorption measurement,respectively.It is found that the flower-like TiO2 nanostructures have a high specific surface area and a large light-harvesting efficiency.The photocatalytical activity of the flower-like anatase TiO2 nanostructures was determined by degradation of methylene blue in aqueous solution,and was compared with commercial P25 titania.It is revealed that the photocatalytical activity of the flower-like anatase TiO2 nanostructures is enhanced a lot.The apparent rate constant of the flower-like anatase TiO2 nanostructures is almost 2 times that of P25 titania.     

Microstructure characterization and photocatalytic activity of mesoporous TiO2 films with ultrafine anatase nanocrystallites

A series of mesoporous TiO₂ films on borosilicate glass with ultrafine anatase nanocrystallites were successfully synthesized using a non-acidic sol gel preparation route, which involves the use of nonionic surfactant Tween 20 as template through a self assembly pathway. The microstructure of these TiO₂ films was characterized by XRD, SEM, HR-TEM, UV-Vis spectroscopy, and N₂ adsorption-desorption isotherm analysis. Their photocatalytic activities were investigated by using creatinine as a model organic contaminate in water. It was found that all mesoporous TiO₂ films prepared with Tween 20 exhibited a partially ordered mesoporous structure. The photocatalytic activity of the TiO₂ films could be remarkably improved by increasing Tween 20 loading in the sol at the range of 50% (v/v), which yielded large amount of catalyst (anatase) on the glass support and enhanced specific surface area. The optimum Tween 20 loading was 50% (v/v) in the sol, above which good adhesion between TiO₂ films and borosilicate glass could not be maintained. The final TiO₂ film (Tween 20: final sol = 50%,v/v) exhibits high BET surface area (∼ 120 m²/g) and pore volume (0.1554 cm³/g), ultrafine anatase nanocrystallinity (7 nm), uniform and crack free surface morphology, and improved photocatalytic activity.     

Controlling the particle size of nanobrookite TiO2 thin films

In this study, pure nanobrookite TiO₂ thin films were successfully deposited on glass substrates with the spin-coating method using titanium butoxide and acetic acid. The particle size of TiO₂ films was controlled by the water:AcAc volume ratio. This study shows that it is possible to obtain single oriented pure brookite films. The structural and optical properties of the nanobrookite TiO₂ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM), spectrophotometer (NKD), and Fourier transform infrared spectrometer (FTIR).     

TiO2 nanocrystal films for sensing applications based on surface plasmon resonance

Spherical and rod shaped organic-capped TiO₂ nanocrystals (NCs), prepared by a hydrolytic route, were deposited as thin films and characterized by means of atomic force microscopy (AFM), X-ray diffraction (XRD) and surface plasmon resonance (SPR). SPR was assessed as transduction technique in order to test the sensing ability of the prepared films for detection of alcohol vapours as a function of NC shape and thermal treatment. The performances of the TiO₂ nanocrystals were found to be dependent on the titania nanocrystal morphology and thermal treatment conditions, pointing to the beneficial effect of a rod-like shape as compared to a spherical one, and to a possible role of the titania surface organic coating in enhancing the sensor response.     

Effect of Nd2O3 addition on the surface phase of TiO2 and photocatalytic activity studied by UV Raman spectroscopy

TiO₂ modified with Nd₂O₃ (Nd-TiO₂) nanoparticles were prepared by a co-precipitation method and utilized as the photocatalysts for the degradation of Rhodamine B (RhB). The influence of Nd₂O₃ on the bulk and surface phase, surface area, particle size, and optical response of TiO₂ was investigated by X-ray diffraction (XRD), UV Raman spectroscopy, transmission electron microscopy (TEM), BET, and UV-visible diffuse reflectance spectra. It is found that the crystalline phase and phase composition in the bulk and surface region of Nd-TiO₂ calcined at high temperatures can be tuned by changing the amount of Nd₂O₃. Based on the results from XPS, EDX, XRD, and UV Raman spectra, it is assumed that Nd³⁺ ions do not enter the TiO₂ lattice, but highly disperse onto the Nd-TiO₂ particle surface in the form of Nd₂O₃ crystallites. These crystallites inhibit the agglomeration, growth in crystal size, and anatase-to-rutile phase transformation of TiO₂. In the photocatalytic degradation of RhB reaction, Nd-TiO₂ nanoparticles with higher surface area and wider optical response are more reactive in case of the same surface anatase phase. When the mixed phases of anatase and rutile exist in the surface region of Nd-TiO₂, the synergetic effect over surface area and optical response is the important parameter which determines optimal photocatalytic activity.     

Effects of pH and polyethylene glycol on surface morphology of TiO2 thin film

In this investigation, a sol gel procedure for preparation of TiO₂ thin films was developed using polyethylene glycol (PEG). Effect of pH on the structure of the films was also investigated. The morphology and surface structure of the films were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). It was found that the films from the base sols had a porous structure and the surface was considerably rough. However, the films made by the acid sols were very dense and had a relatively smoother surface. It was also found that by using PEG, the surface area of the film became larger as a result of the increase in the film porosity. BET analysis confirmed the increase in the surface area which enhanced the photocatalytic activity of TiO₂ thin film in degradation of Malachite Oxalate Green.     

Laser-induced enhancement of the surface hardness of nanoparticulate TiO2 self-cleaning layer

We here report that the abrasion resistance of nanoparticulate TiO₂ self-cleaning layers can be highly enhanced without a considerable loss of photocatalytic capability. TiO₂ coating layers solution-deposited onto the glass substrate were irradiated by a pulsed ultraviolet (UV) laser at 355 nm, which modified the surface morphologies via laser-induced local melting of TiO₂ nanoparticles. The surface hardness, measured by pencil scratch test, improved with increasing laser power (P). While an unmodified TiO₂ layer revealed a hardness of 6B, it increased to 2H after the surface was irradiated at P = 0.3 W. Almost all of the stearic acid deposited on an unmodified sample disappeared after UV exposure for 12 h. The photocatalytic decomposition was slowed down on laser-irradiated TiO₂ surfaces and this is attributed to the reduction of specific surface areas as a result of the morphological modifications. However, a TiO₂ layer hardened to 2H still exhibited fairly good photocatalytic activity, decomposing more than 75% of the stearic acid after exposure for the same duration.     

Calcination/acid-activation treatment of an anodic oxidation TiO<Subscript>2</Subscript>/Ti film catalyst

The aim of this work was to investigate the effects of calcination/acid-activation on the composition, structure, and photocatalytic (PC) reduction property of an anodic oxidation TiO₂/Ti film catalyst. The surface morphology and phase composition were examined by scanning electron microscopy and X-ray diffraction. The catalytic property of the film catalysts was evaluated through the removal rate of potassium chromate during the PC reduction process. The results showed that the film catalysts were composed of anatase and rutile TiO₂ with a micro-porous surface structure. The calcination treatment increased the content of TiO₂ in the film, changed the relative ratio of anatase and rutile TiO₂, and decreased the size of the micro pores of the film catalysts. The removal rate of potassium chromate was related to the technique parameters of calcination/acid-activation treatment. When the anodic oxidation TiO₂/Ti film catalyst was calcined at 873 K for 30 min and then acid-activated in the concentrated H₂SO₄ for 60 min, it presented the highest catalytic property, with the removal rate of potassium chromate of 96.3% during the PC reduction process under the experimental conditions.     

SnO2@TiO2核-壳纳米线的制备及其光催化性能研究

本文通过固-液-气(VLS)生长机制,利用化学气相沉积法(CVD)制备SnO₂纳米线。利用原子层沉积(ALD)以钛酸四异丙酯为前驱体在SnO₂纳米线表面沉积不同厚度的TiO₂壳层,形成SnO₂@TiO₂核-壳纳米线结构。通过中间Al₂O₃插层,分别制备出金红石和锐钛矿两种不同晶型的TiO₂,从而制备出两种不同复合结构的SnO₂@TiO₂核-壳纳米线。实验研究该复合结构中TiO₂的厚度与晶型对紫外光下光催化降解甲基橙溶液活性的影响。     

ZnO and TiO2 1D nanostructures for photocatalytic applications

ZnO and TiO₂ 1D nanostructures (nanorods and nanotubes) were prepared by low-cost, low-temperature, solution-based methods and their properties and photocatalytic performance were studied. ZnO nanorod samples with titania and alumina shells were also prepared by solution-based methods, and their properties and photocatalytic performance were compared to that of bare ZnO nanorods. We found that ZnO and TiO₂ exhibited comparable photocatalytic performance. Faster dye degradation under simulated solar illumination was observed for ZnO, while under UV illumination faster degradation was observed for TiO₂. ZnO nanorods with titania shells exhibited inferior photocatalytic performance, while for alumina shells the performance was similar to bare ZnO. Reasons for observed differences are discussed, and the effect of the shell on photocatalytic activity is attributed to the changes in native defects at the ZnO surface/shell interface.     

Characterization of microstructure of Nano-TiO2 coating deposited by vacuum cold spraying

Control of the microstructure of TiO₂ coatings through preparation methods significantly influences the coating performance. In this study, a vacuum cold-spray process, as a new coating technology, is used to deposit nanocrystalline TiO₂ coatings on conducting glass and stainless steel substrates. TiO₂ deposits were formed using two types of nanocrystalline TiO₂ powders with mean particle diameters of 200 and 25 nm. Coating microstructures were characterized by scanning electron microscopy and x-ray diffraction analysis. Results demonstrate that a thick nanocrystalline TiO₂ coating can be deposited by the vacuum cold-spray process. The coating was found to consist of particles stacked as agglomerates that build up to several hundred nanometers. The coating also presents a mesoporous microstructure that could be effective in such applications as photocatalytic degradation and dye-sensitized solar cells. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Effect of Cu2+ doping on photocatalytic performance of liquid flame sprayed TiO2 coatings

Cu²⁺ was added to liquid feedstock to deposit ion doping TiO₂ photocatalytic coatings through liquid flame spraying. The coating microstructure was characterized by x-ray diffraction (XRD), transmission electron microscopy, and x-ray photoelectron spectroscopy (XPS). The photocatalytic performance of coatings was examined by photodegradation of acetaldehyde. The XRD analysis shows that the crystalline structure of coatings is not significantly influenced by Cu²⁺ doping. The photocatalytic activity of the TiO₂ coatings is enhanced by Cu²⁺ doping. It is found that a high concentration of Cu²⁺ doping decreases the activity. The XPS analysis shows that the adsorbed oxygen concentration is increased with the increase of Cu²⁺ dopant concentration and decreases with a further increase of dopant concentration. The enhancement of photocatalytic activity can be attributed to the adsorption ability of oxygen and other reactants on the surface of doping TiO₂ coatings. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.