Macroporous TiO2/carbon composites prepared via a simple soaking process

A new-type composite photocatalyst of three-dimensional ordered macroporous (3DOM) TiO₂/C was prepared and tested in this paper. 3DOM carbon materials were first prepared by colloidal crystal templating process, and then the sols of TiO₂ from tetrabutyl titanate were infiltrated in the macroporous structures via capillary force. After calcinations at nitrogen flow, TiO₂/C composite materials were prepared. The obtained samples were analyzed by SEM, TEM, XRD and BET. The results indicated that macroporous TiO₂/C can remain the three-dimensional ordered structure and TiO₂ nanoparticles distributed in the interior of macropores uniformly. Eventually, 3DOM TiO₂/C materials were used as a new-type photocatalysts to decompose the methyl orange solution under ultraviolet light, which displayed excellent catalytic activity and regenerative ability.     

Properties of TiO2 prepared by acid treatment of BaTiO3

TiO₃ powders were prepared by acid treatment of BaTiO₃ and their properties were investigated. The BaTiO₃ powder was subjected to HNO₃ in concentrations ranging from 10⁻³ to 8 M at 90 °C for 0.5-6 h. Dissolution of BaTiO₃ and precipitation of TiO₂ occurred at acid concentrations of 2-5 M. BaTiO₃ dissolves completely to form a clear solution at reaction times of 0.5-1 h, but a rutile precipitate is formed after 2 h of acid treatment. By contrast, anatase is precipitated by adjusting the pH of the clear solution to 2-3 using NaOH or NH₄OH solution. The rutile crystals were small and rod-shaped, consisting of many small coherent domains connected by grain boundaries with small inclination angles and edge dislocations, giving them a high specific surface area (S_BET). With increasing HNO₃ concentration, the S_BET value increased from 100 to 170 m²/g while the crystallite size decreased from 25 to 11 nm. The anatase crystals obtained here were very small equi-axial particles with a smaller crystallite size than the rutile and S_BET values of about 270 m²/g (higher than the rutile samples). The photocatalytic activity of these TiO₂ was determined from the decomposition rate of Methylene Blue under ultraviolet irradiation. Higher decomposition rates were obtained with larger crystallite sizes resulting from heat treatment. The maximum decomposition rates were obtained in samples heated at 500-600 °C. The photocatalytic activity of the TiO₂ was found to depend more strongly on the sample crystallite size than on S_BET.     

Crack formation in TiO2 films prepared by sol-gel processing: Quantification and characterization

TiO₂ thin films were prepared by dip-coating from soluble precursor powders using different solvent mixtures. Under certain conditions cracking occurs during drying and thermal treatment. Both extent of damage and time of formation were evaluated from micrographs using image processing software. Different approaches for data evaluation are applied and compared. It is shown that reproducible measurements of defect densities are a useful tool for the optimization of process parameters.Data indicate that the presence of 1,5-pentanediol retards the formation of a rigid xerogel network that is responsible for crack formation during film drying. The air moisture during dip-coating also turns out to have a systematic effect on the microstructure of the densifying film as demonstrated by quantitative defect analysis. This method has to be used carefully, though, that a qualitative change of the damage pattern does not lead to a misinterpretation of the data.     

低压化学气相沉积MoSi2涂层微观结构及氧化性能

为了防止Mo合金的高温氧化,本研究采用低压化学气相沉积技术在Mo合金表面制备MoSi2抗氧化涂层,借助X射线衍射仪、扫描电镜及能谱仪等分析手段,对涂层的微观结构进行了研究,测试了涂层的抗氧化和抗热震性.结果表明:MoSi2涂层结构致密,仅有少量微裂纹存在,表现出良好的抗热震和抗氧化性能;经20次1300℃-室温循环热震实验后,涂层未出现开裂与脱落现象;涂层试样在1300℃氧化气氛下氧化180 h,失重率小于0.83%,分析揭示了涂层试样氧化失重的主要原因为氧扩散通过涂层与Mo基体发生反应,生成极易挥发的MoO、MoO2、MoO3,氧在涂层中的扩散速率决定了涂层的失重速率.     

Structural and electrochromic properties of TiO2 thin films prepared by metallorganic chemical vapor deposition

Titanium dioxide thin films were deposited by Metallorganic Chemical Vapor Deposition at substrate temperatures ranging from 250 °C to 450 °C over soda lime glass and indium tin oxide coated glass substrates. X-ray diffraction studies show that films have a crystalline anatase structure at all the deposition temperatures. Particle size decreases and texture changes with the increase in substrate temperature. X-ray photoelectron spectroscopy confirms the appearance of a new well resolved state in the core level of Ti 2p spectrum shifted by 1.16 eV to lower binding energy due to the reduction of Ti^+ 4 to Ti^+ 3 upon litheation. Chronoamperometery, cyclic voltammetery and in situ UV-Vis spectrophotometeric studies were carried out on the prepared samples. Particle size and crystallinity control the electrochromic performance. The 350 °C film shows the highest ion storage capacity and the highest optical modulation along with an appreciable band gap broadening.     

一种多功能有机蒙脱土-纳米TiO2/环氧树脂复合材料

将有机蒙脱土（O-MMT）和纳米TiO₂共同复合到环氧树脂中,成功地制备出了一种高性能多功能O-MMT-纳米TiO₂/环氧树脂复合材料。由XRD检测结果和TEM观察结果证实,由于利用了O-MMT、纳米TiO₂与环氧树脂间的相互作用,蒙脱土（MMT）层被高度剥离,所得的二维MMT纳米单片与零维纳米TiO₂颗粒交错分布于树脂基体中。力学性能测试、热分析和耐沾污性试验表明,O-MMT-纳米TiO₂/环氧树脂复合材料的多项性能都比纯环氧树脂有大幅提高。     

Photocatalytic performance of very thin TiO2/SnO2 stacked-film prepared by magnetron sputtering

TiO₂/SnO₂ stacked-layers are synthesized by reactive sputter deposition on the glass substrate. Very thin TiO₂/SnO₂ bilayer-photocatalysts exhibited a very high photocatalytic activity for a degradation of gaseous acetaldehyde. Both the control of an electronic structure of TiO₂ overlayer in the near-surface region and the interfacial separation of photogenerated electrons/holes in the TiO₂/SnO₂ stacked-layer are keys to improve the photocatalytic performance.     

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.     

Characterization of SiO2 and TiO2 films prepared using rf magnetron sputtering and their application to anti-reflection coating

Preparation of TiO₂ and SiO₂ films for optical applications was attempted using conventional rf magnetron sputtering in the sputtering ambient with various O₂/Ar+O₂ ratios and at substrate temperatures between room temperature and 400 °C. X-ray photoelectron spectroscopy (XPS) and optical spectroscopy investigations indicated that oxygen addition in the sputtering ambient was essential for growing TiO₂ films with stoichiometric compositions and good transmittance, while SiO₂ films had a stoichiometric composition of O/Si ratio=2.1-2.2 and were highly transparent in the visible wavelength region, independent of gas composition in the growing ambient. It was also identified from scanning electron microscope (SEM), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FTIR) measurements that the structural characteristics of both TiO₂ and SiO₂ films were significantly improved with O₂ addition in the sputtering ambient, showing smoother surface morphologies and higher resistances to water absorption when compared with films grown without O₂ addition. Heating of the substrate between 200 and 400 °C considerably increased the refractive index of TiO₂ layers, resulting in dense structures along with an improvement of crystallinity. For optical applications, AR coatings composed of 2-4 multi-layers on glass were designed and manufactured by stacking in turn the SiO₂ and TiO₂ films at room temperature and O₂/Ar+O₂=10%, and the performance of the produced coatings was compared with simulation results.     

A low-temperature process to synthesize rutile phase TiO2 and mixed phase TiO2 composites

This works employed K₂Ti₄O₉, a novel Ti source, to prepare TiO₂ powders. By a “low-temperature dissolution-reprecipitation process” (LTDRP), rutile phase TiO₂ was successfully synthesized after reacting at 50 °C for 48 h. The obtained sample showed a specific surface area about 45 m²/g, and excellent activity in photo-destruction of NO_x gas. The coupling of rutile phase TiO₂ with commercial anatase TiO₂ showed significant effect in further enhancing the photocatalytic activity.     

Thermal stability and tensile properties of sol-enhanced nanostructured Ni–TiO2 composites

A highly-dispersed TiO₂ nano-particles reinforced Ni–TiO₂ composite was prepared by sol-enhanced composite electroplating. The microstructure, thermal stability and tensile properties of the sol-enhanced and traditional Ni–TiO₂ composites were explicitly compared. TiO₂ nano-particles agglomerated to large clusters of ∼400 nm in the traditional Ni–TiO₂ composite. In contrast, nano-sized TiO₂ particles (∼15 nm) were distributed at grain boundaries in the sol-enhanced composite. The grain size, higher micro-strain (∼0.31%) and higher microhardness (∼407 HV₅₀) of the sol-enhanced Ni–TiO₂ composite were stabilized up to 250 °C compared to 150 °C of the traditional composite. The sol-enhanced Ni–TiO₂ composite showed a much higher tensile strength of ∼1050 MPa compared to ∼610 MPa of the traditional composite. The lattice diffusion dominated at high temperatures during grain growth for the sol-enhanced composite. The distribution and location of TiO₂ nano-particles played a significant role in determining the thermal stability and tensile behaviors.     

Photo-fixation of SO2 in nanocrystalline TiO2 films prepared by reactive DC magnetron sputtering

We report on photo-fixation of SO₂ onto nanostructured TiO₂ thin films prepared by reactive DC magnetron sputtering. The films were exposed to 50 ppm SO₂ gas mixed in synthetic air and illuminated with UV light at 298 and 473 K. The evolution of the adsorbed SO_x species was monitored by in situ Fourier transform infrared specular reflection spectroscopy. Significant photo-fixation occurred only in the presence of UV illumination. The SO₂ uptake was dramatically enhanced at elevated temperatures and then produced strongly bonded surface-coordinated SO_x complexes. The total SO_x uptake is consistent with Langmuir adsorption kinetics. The sulfur doping at saturation was estimated from X-ray photoelectron spectroscopy to be ~ 2.2 at.% at 473 K. These films were pale yellowish and had an optical absorption coefficient being ~ 3 times higher than in undoped film. The S-doped films exhibit interesting oleophobic properties, exemplified by the poor adherence of stearic acid. Our results suggest a new method for sulfur doping of TiO₂ to achieve combined anti-grease and photocatalytic properties.     

SiO2/TiO2 thin films with variable refractive index prepared by ion beam induced and plasma enhanced chemical vapor deposition

SiO₂/TiO₂ optical thin films with variable compositions have been prepared by ion beam induced and plasma enhanced chemical vapour deposition (IBICVD and PECVD). While the films obtained by IBICVD were very compact, the PECVD ones with a high content of Ti presented a columnar microstructure. The formation of Si–O–Ti bonds and a change in the environment around titanium from four- to six-coordinated has been proved by vibrational and X-ray absorption spectroscopies. The refractive index increased with the titanium content from 1.45 to 2.46 or 2.09 for, respectively, the IBICVD and PECVD films. Meanwhile, the band gap decreased, first sharply and then more smoothly up to the value of pure TiO₂. It is concluded that the optical properties of SiO₂/TiO₂ thin films can be properly tailored by using these two procedures.     

Ag surfactant effects of TiO2 films prepared by sputter deposition

The surfactant effect of Ag on the thin film structure of TiO₂ by radio frequency magnetron sputtering has been investigated. Comparisons between the atomic force microscopy images revealed that the surface roughness of TiO₂ film mediated by Ag was smaller than that of the TiO₂ film without Ag. The surface segregation effect of Ag was confirmed using X-ray photoelectron spectroscopy. The results of X-ray diffraction revealed that the initial deposition of a 0.4 nm thick Ag surfactant layer onto a Fe buffer layer prior to the deposition of the TiO₂ film reduced the rutile (110) growth and enhanced the anatase (100) growth. It was concluded that Ag was an effective surfactant for changing the thin film structure of TiO₂ on the Fe buffer layer. The photocatalytic effect of the fabricated TiO₂ film was also investigated using the remote oxidation process. TiO₂ films with the Ag surfactant exhibited higher photocatalytic activity than conventionally deposited TiO₂ films.     

Spectroscopic ellipsometry of TiO2 layers prepared by ion-assisted electron-beam evaporation

Single layer TiO₂ films deposited on BK7 glass substrates by the ion-assisted electron-beam evaporation technique have been characterized by phase modulated spectroscopic ellipsometry. The ellipsometry spectra were recorded in the wavelength range of 300–1000 nm. The measured spectra were then fitted with theoretically simulated curves generated assuming different model sample structures. Analyses were carried out separately in three different wavelength regimes, the transparent regime with no dispersion of refractive index (650–1000 nm), the transparent regime with dispersion of refractive index (400–650 nm) and the absorbing regime (300–450 nm). Modeling has been attempted with both homogeneous and inhomogeneous sample structures. For the inhomogeneous structure, both linear and non-linear variation of refractive index along the depth of the sample were used. Refractive indices of the samples were determined separately from the best-fit ellipsometric data in the above three wavelength regimes. Finally, variation of refractive index with the variation in ion beam currents has been studied.     

Investigation on solar photocatalytic activity of TiO2 loaded composite: TiO2/Eggshell, TiO2/Clamshell and TiO2/CaCO3

The TiO₂/Eggshell, TiO₂/Clamshell and TiO₂/CaCO₃ loaded composites were prepared by sol-gel method and characterized by XRD and SEM. Their photocatalytic activities were measured through the degradation of Acid Red B under solar light irradiation. The influences of TiO₂ loaded content, heat-treated temperature and time on the photocatalytic activities were reviewed. The effects of irradiation time and dye initial concentration on the photocatalytic degradation were also investigated. The results showed that the photocatalytic activity can be greatly enhanced by appropriate TiO₂ loaded content.     

Photocatalytic Zn-doped TiO2 films prepared by DC reactive magnetron sputtering

Zn-doped TiO₂ films were prepared by means of pulsed DC reactive magnetron sputtering method using Ti and Zn mixed target. The deposition condition was optimized to produce uniform and transparent TiO₂ films. Titanium was in the Ti⁴⁺ oxidation state in all Zn-doped TiO₂ films. The zinc oxide deposited on the substrate was in the fully oxidized state of ZnO. Increase of zinc concentration inhibited the crystal growth in the TiO₂ films. The surface morphology gradually changed from crystalline to amorphous along with the increase of doped zinc concentration. The optical transmittances of these films decreased only slightly with increasing zinc concentration due to very similar band edges of ZnO and anatase TiO₂. The doped ZnO had weak influence on light absorption of the TiO₂ films. When zinc concentration was very low (<1 at%), the photocatalytic activities of the doped films had nearly no difference from that of pure TiO₂ film. Photocatalytic activities decreased obviously in the films containing high amount of zinc oxide.     

A soft chemical synthesis of TiO2 nanobelts

Single crystal TiO₂ nanobelts have been synthesized in large scale via a simple soft chemical process. The lengths of the nanobelts are up to several tens of micrometers, and the widths are in the range of 150 to 700 nm. X-ray powder diffraction studies show that the as-prepared TiO₂ nanobelts are composed of a pure anatase phase. High-resolution transmission electron microscopy investigations show that the linear growth of nanobelts is along the [001] direction of the anatase structure. A rational mechanism has been proposed for the growth of TiO₂ nanobelts based on the detailed analysis of the structure of anatase phase TiO₂. The present study has enlarged the family of nanobelts, and offers a possible soft chemical route to one-dimensional crystalline nanobelts.     

Cathodoluminescence of TiO2 nanotubes prepared by low-temperature anodization of Ti foils

We show that anodization of Ti sheets in an ethylene glycol and HF containing electrolyte at temperatures under 0 °C results in the formation of a self-arranged ordered porous structure at the top surface of the sample. This perforated surface structure initiates the growth of an ordered array of titania nanotubes. The inner diameter of nanotubes can be modified in a controlled fashion in the range from 10 nm to more than 250 nm through the change of the electrolyte temperature from −20 °C to + 50 °C. The spectral distribution of cathodoluminescence from a cluster of nanotubes clearly demonstrates the formation of resonator modes which are separated from each other by around 200 meV.     

Fabrication of polycrystalline TiO2 nanopatterns by TiO2 sol base imprint lithography

This paper reports a process for fabricating TiO₂ nano-patterns using nanoimprint lithography and a sol–gel method. An ethanol-based TiO₂ sol was prepared using tetrabutylorthotitanate as a precursor and used as an imprint resin. A replicated polydimethylsiloxane (PDMS) mold was used as an imprint stamp. During the imprinting process at 5 atm and 200 °C for 1 h, the TiO₂ sol changed to a TiO₂ gel by absorbing the solvent into the PDMS mold. After imprinting, a TiO₂ gel pattern was formed on an oxidized Si wafer. After subsequent annealing, it confirmed that patterns of the master template were transferred to TiO₂ patterns by Scanning Electron Microscopy. Furthermore, Transmission Electron Microscopy and X-Ray Diffraction showed that the TiO₂ gel patterns had been converted to an inorganic polycrystalline TiO₂ pattern.