Ab initio calculations of electronic structure of anatase TiO2

This paper presents the results of the self-consistent calculations on the electronic structure of anatase phase of TiO2. The calculations were performed using the full potential-linearized augmented plane wave method (FP-LAPW)in the framework of the density functional theory (DFT) with the generalized gradient approximation (GGA). The fullyoptimized structure, obtained by minimizing the total energy and atomic forces, is in good agreement with experiment.We also calculated the band structure and the density of states. In particular, the calculated band structure prefers an indirect transition between valence and conduction bands of anatase TiO2, which may be helpful for clarifying theambiguity in other theoretical works.     

Formation Process of a TiO2 Inverse Opal

Inverse opals of TiO2 with different filling fractions were fabricated by using an opal of polystyrene spheres as a template.Scanning electron microscopy showed the accumulative process of TiO2.The transmission spectra of inverse opals with different filling fractions were measured and the shifts of transmission dip with the filling fraction were observed.Our investigation made the infiltration process clear,and it might be helpful for further improvement of the fabrication of TiO2 inverse opals.     

TiO2–carbon nanotube composites for visible photocatalysts – Influence of TiO2 crystal structure

We investigated the influence of the crystal structure of TiO₂ and the use of different TiO₂ precursors on the properties and photocatalytic activity of carbon nanotube (CNTs)–titania composites. We found that the crystal structure and properties of starting TiO₂ nanomaterial significantly affected the effect of CNTs incorporation on the photocatalytic activity under simulated solar and visible light illumination (simulated solar illumination with UV-blocking filter). In case of significant photocatalytic activity under visible light illumination (anatase TiO₂), likely due to the presence of native defects, composites exhibited lower activity under visible illumination only, but higher activity under simulated solar illumination. The opposite trends were observed for P25 (anatase + rutile) and rutile TiO₂, where incorporation of CNTs resulted in a significant increase of photocatalytic activity under visible illumination. Thus, control over crystal structure and native defects is essential for the development of efficient visible light activated photocatalysts.     

Unusual oxygen re-equilibration kinetics of TiO2−δ

Oxygen re-equilibration kinetics, along with the equilibrium conductivity, have been measured on undoped, single-crystal TiO_2−δ, by a four-probe d.c. conductivity relaxation technique, against oxygen partial pressure in the range of − 16 < log(P_O2/atm) ≤ 0 at different temperatures in the range of 1173 ≤ T/K ≤ 1373. The isothermal conductivity varies as σ ∝ P_O2^m with m ≈ − 1/4, − 1/5 and − 1/6 in turn with increasing P_O2 up to 1 atm, suggesting a sequential variation of the majority ionic disorder types from Ti_i to Ti_i to V_O, respectively. Contrary to the conventional knowledge that due to the local (defect) equilibrium postulate there should be one and only one chemical diffusivity or single relaxation time for a binary oxide, the oxygen re-equilibration kinetics has turned out to be twofold with two different relaxation times depending on oxygen activities. This is interpreted as being due to the independent relaxation of each sublattice of TiO₂ in an oxygen activity gradient applied, indicating a failure of local equilibrium during oxygen re-equilibration. From the two different relaxation times the chemical diffusion coefficients of component Ti and O are separately evaluated and subsequently, their self-diffusion coefficients. The latter are found to be in a good agreement with the literature data.     

Elastic Properties of Rutile TiO2 at High Temperature

Dependence of elastic properties on temperature for rutile TiO2 is investigated by the Cambridge Serial Total Energy Package （CASTEP） program in the frame of density function theory （DFT） and the quasi-harmonic Debye model The six independent elastlc constants of rutile TiO2 at high temperature are theoretically obtained for the first time. It is found that with increasing temperature, the elastic constants will decrease monotonically. Moreover, we successfully obtain the polycrystalline moduli BH and GH, as well as the Debye temperature ⊙D.     

Effects of heat treatment and TiO2 content on the optical properties of Eu3+ doped TiO2–SiO2 thin films

The photoluminescence properties of Eu³⁺-doped TiO₂–SiO₂ thin films were investigated. The films were deposited on silicon substrates by the sol–gel process using the dip-coating method. The molar ratio of TiO₂ content was varied from 25% to 100%, while Europium concentration was fixed to 1%. The obtained films were calcinated at various temperatures ranging from 400 °C to 1300 °C, which allowed determining the optimal conditions for the Eu³⁺ luminescence. Meanwhile, the structure of TiO₂–SiO₂ powders, prepared in the same conditions as the films, was also studied by Raman spectroscopy. It revealed the role of Europium and SiO₂ on the stabilization of the anatase phase and the importance of the silica matrix in the control of titania particle size.     

Extraction of optical constants and thickness of nanometre scale TiO2 film

TiOTiO2 薄膜 沉积物 磁电管喷射系统 X射线 发射光谱TiO₂ thin films, pointwise constrained optimization approach, constrained nonlinear programming, optical constants, parameters extractionProject supported by Shanghai Municipal Commission for Science and Technology (Grant No 03DZ14025) and National Basic Research Program of China (Grant No 2006CB300406).3/4/2005 12:00:00 AM2005-03-042005-07-28TiO2 thin films were deposited on glass substrates by sputtering in a conventional rf magnetron sputtering system. X-ray diffraction pattern and transmission spectrum were measured. The curves of refraction index and extinction coefficient distributions as well as the thickness of films calculated from transmission spectrum were obtained. The optimization problem was also solved using a method based on a constrained nonlinear programming algorithm.     

Effect of Process Parameters on Laser Damage Threshold of TiO2 Coatings

We investigate the laser damage behaviour of an electron-beam-deposited TiO2 monolayer at different process parameters. The optical properties, chemical composition, surface defects, absorption and laser-induced damage threshold （LIDT） of films are measured. It is found that TiO2 films with the minimum absorption and the highest LIDT can be fabricated using a TiO2 starting material after annealing. LIDT is mainly related to absorption and is influenced by the non-stoichiometric defects for TiO2 films. Surface defects show no evident effects on LIDT in this experiment.     

Photocatalytic Properties of TiO2/Si-NPA Nano Composite Systems

A new composite system is fabricated by depositing the TiO2 film on a silicon nanoporous pillar array （Si-NPA） and annealing at 500℃ using the spin coating method. Such a composite system exhibits a uniform morphology with the micron-dimension pillar array. Photocatalytic properties are investigated based on the degradation of methyl orange dye solution, and the results show that the photocatalytic efficiency of such a nano-composite system is 1.7 times that of the TiO2/glass system. The enhancement of photocatalytic efficiency is attributed to the large surface area of the TiO2/Si-NPA system.     

Investigation of hydrogen storage in MWCNT–TiO2 composite

The hydrogen storage capacity of MWCNT–TiO₂ composite has been evaluated in the present work. The composite has been prepared by means of ultrasonication followed by drop casting on substrates. Morphology, structural and functional group studies of the prepared samples are carried out by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. Then, the samples are hydrogenated in the hydrogenation chamber as a function of time. Hydrogen storage capacity of the composite sample is found to be 0.9 wt% at 100 °C. Hydrogen uptake of the composite is accounted for the spillover mechanism in CNTs–metal oxide composite. Desorption temperature range, activation energy of desorption, binding energy of hydrogen are determined from thermogravimetric (TG) analysis.     

Study of refractive index and thickness of TiO2／ormosil planar waveguide

Hybrid titania/ormosil waveguide films have been prepared by sol-gel method at low thermal treatment temperature of 150℃. The influence of processing parameters including the molar ratios of Ti(OBu)_{4}/glycidoxypropyltrimethoxysilane (GLYMO) and H_{2}O/Ti(OBu)_{4} (expressed as R), especially aging of sol, on the refractive index and thickness of film was investigated. The optical properties of films were measured with Scanning Electron Microscope and m-line spectroscopy. The results indicate that the film thickness increases with the aging time of sol, but the variation of refractive index as a function of aging time of sol depends on the relative ratio of GLYMO to Ti-alkoxide. The relation between film thickness and corresponding sol viscosity is linear as the volume of GLYMO is 80% within the range of measured data.     

Temperature Dependence of the Fluorescence Emission Intensity of Eu/TiO2 Nanocrystals

The samples of europium ions doped titanium dioxide （Eu^3＋/TiO2） nanocrystals are synthesized by a modified sol-gel method with hydrothermal treatment. The x-ray diffraction and scanning electron microscopy are used to characterize the sample. The temperature-dependent fluorescence emission effect of Eu^3＋-doped samples is investigated. It is found that under the excitation of 514.5nm light, the emission intensity of Eu^3＋ reaches a maximum value at 450K among various Eu^3＋ dopant concentrations in Eu^3＋ /TiO2 nanocrystals. The variation of the emission intensity may be attributed to the photon-assist absorption and the temperature-quenching effect.     

Effects of Different Dispersion Methods on the Microscopical Morphology of TiO2 Film

Nanocrystalline porous TiO2 films were prepared on conducting glass supports （ITO） by processed commercial TiO2 nanometre powder （P25）. Three methods of physical dispersing for TiO2 powder, i.e. grinding, magnetic stirring, sonicleaning, were used to disperse TiO2 nanometre powder. Surface morphologies of TiO2 films were observed by optic-microscope and SEM. It is found that the surface morphologies of TiO2 films are determined not only by the dispersing methods but also by the percentage of TiO2 powder in the dispersing system. Different film morphologies can be obtained under the same preparation condition but with different dispersing methods. A lot of cracks exist on the film surface for which the TiO2 slurry is dispersed by grinding. Magnetic stirring leads to some white points and micro-holes on the film surface. Only a few of micro-holes can be observed on the film surface, in which the TiO2 slurry is dispersed by sonicleaning. Different surface morphologies can also be found with different thicknesses of TiO2 films. Different film thicknesses are due to different percentages of TiO2 powder in the slurry. The related mechanism leading to different features of the surface morphologies for the TiO2 films is discussed.     

Effect of Microstructure of TiO2 Thin Films on Optical Band Gap Energy

TiO2 coatings are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for four hours, the spectra and XRD patterns of TiO2 thin film are obtained. XRD patterns reveal that only anatase phase can be observed in TiO2 coatings regardless of the different annealing temperatures, and with the increasing annealing temperature, the grain size gradually increases. The relationship between the energy gap and microstructure of anatase is determined and discussed. The quantum confinement effect is observed that with the increasing grain size of TiO2 thin film, the band gap energy shifts from 3.4 eV to3.21 eV. Moreover, other possible influence of the TiO2 thin-film microstructure, such as surface roughness and thin film absorption, on band gap energy is also expected.     

Preparation of TiO2 Inverse Opal via a Modified Filling Process

By applying polystyrene opals made by a vertical deposition method as the templates, a modified filling method and a well-controlled calcination process, we have successfully obtained a large-area ordered TiO2 inverse opal with a higher vo]ume fraction (14.5%) and a visib]e photonic bandgap. The influences of the fi]]ing process and calcination conditions on the fabrication of the TiO2 inverse opal are investigated.     

Study on the optical properties of PPV／TiO2 nanocomposites

The optical properties of poly(Phenylenevinylene)(PPV)/TiO2 nanocomposites,prepared via the sol-gel process,were investigated by UV-VIS,FT-IR,FL spectroscopy and TEM.TEM images indicated that the surfaces of TiO2 nanoparticles became rough,and finally formed the connected network as the TiO2 content increased.FT-IR spectra showed the titanium butoxide hydrolyzed to from Ti organic compound,which can result in the connected network of TiO2 nanoarticles.The conjugation of PPV polymer chains can be interrupted by the TiO2 network structure,as evdenced in UV-VIS spectra.The investigation of the PL spectra revealed that the emitted light of the PPV/TiO2 nanocoposites blue shifted wihout fine structure,and the PL intensity enhanced,when the TiO2 net work fromed.These phenomena suggested that the optical properties of the PPV/TiO2 nanocomposites were dependent on the interfacial structure between PPV and TiO2 nanoparticles.2001 Elsevier Science B.V.All rights reserved.     

Photocatalytic disinfection of water with Ag–TiO2 nanocrystalline composite

A method of solution impregnation and calcination has been demonstrated for synthesizing nanoparticles of Ag–TiO₂ composite photocatalysts for use in the disinfection of water. Only a small proportion of the TiO₂ surface is covered by nano-islands of Ag corresponding to a loading of 4 wt.% of Ag; thus, most of the TiO₂ surface is available for photocatalytic function. Although the primary particles of both Ag and TiO₂ are in the 10- to 20-nm range, microscopic studies indicate that the primary particles of Ag are deposited on nano-agglomerates of 30- to 70-nm-sized TiO₂. It is seen that the relatively small loading of Ag has not caused any UV–vis spectral shift but has enhanced the rate of photocatalytic antibacterial action of TiO₂, presumably by electron trapping.     

Influence of Yb-Doped Nanoporous TiO2 Films on Photovoltaic Performance of Dye-Sensitized Solar Cells

Yb-doped TiO2 pastes with different Yb/TiO2 weight ratios are prepared in the sol-gel process to obtain dyesensitized solar cells （DSCs）. The nanocrystalline size of Yb-TiO2 becomes smaller and the lattice parameters change. Lattice distortion is observed and dark current is detected. It is found that a part of Yb existing as insulating oxide Yb2O3 state acts as barrier layers at the electrode-electrolyte interface to suppress charge recombination. A Yb-doped TiO2 electrode applied in DSCs leads to a higher open-circuit voltage and a higher fill factor. How the Yb-doped TiO2 films affect the photovoltaic response of DSCs is discussed.     

Enhanced photocatalytic performance of TiO2 particles via effect of anatase–rutile ratio

In the present work anatase–rutile transformation temperature and its effect on physical/chemical properties as well as photocatalytic activity of TiO₂ particles were investigated. The characterisation of the synthesised and annealed TiO₂ particles were determined by X-Ray Powder Diffraction (XRD), scanning electron microscope (SEM), dynamic light scattering (DLS) and Brunauer–Emmett–Teller surface area analysis (BET). The refraction in the ultraviolet–visible (UV–vis) range was assessed using a dual-beam spectrophotometer. The photocatalytic performance of the particles was tested on methylene blue solution. The XRD data indicated that the percentage of rutile increased with the annealing temperature and almost 100% of anatase transformed to rutile at 1000 °C. In addition, the phase transformation was a linear function of annealing temperature so phase composition of TiO₂ can be controlled by changing the annealing temperature. The SEM and BET results presented the increase of agglomerate size and the decrease of specific surface area with the increasing annealing temperature. This proved that anatase has smaller particle size and higher surface area than rutile. The photocatalytic activity of the annealed TiO₂ powders reduced with the increase of annealing temperature. The samples annealed at 900 °C and 925 °C with anatase: rutile ratio of 92:8 and 77:23, respectively, showed the best activity. These results suggested that the photocatalytic activity of TiO₂ particles is a function of phase composition. Thus it can be enhanced by changing its phase composition which can be controlled by annealing temperature.     

Effects of γ rays irradiation on structure and property of TiO2 thin films

TiO₂ thin films were deposited on a glass substrate by the radio frequency magnetron sputtering method, and annealed for 2 h at temperatures of 550°C. Then, ⁶⁰Co γ rays with different doses were used to irradiate the resulting TiO₂ thin films. The surface features of films before and after irradiation were observed by scanning electron microscope (SEM). Simultaneously, the crystal structure and optical properties of films before and after irradiation were studied by X-ray diffraction (XRD), UV–VIS transmission spectrum and Photoluminescence (PL) spectrum, respectively. The SEM analysis shows that the film is smooth with tiny particles on the film surface, and non-crystallization trend was clear after irradiated with γ rays. The XRD results indicated that the structure of the film at the room temperature mainly exists in the form of amorphous and mixed crystal at a sputtering power of 200 W, and non-crystallinity was more obvious after irradiation. Obvious difference can be found for the transmissibility of the irradiated and pre irradiation TiO₂ films by the UV-VIS spectra. The color becomes light yellow, and the new absorption edge also appeared at about 430 nm. PL spectra and photocatalysis experiments indicate that the photocatalysis degradation rate of the TiO₂ films on methylthionine chloride solution irradiated with the maximum dose can be increased to 90%.