Thermostable photocatalytically active TiO<Subscript>2</Subscript> anatase nanoparticles

Anatase is the low-temperature (300–550 °C) crystalline polymorph of TiO₂ and it transforms to rutile upon heating. For applications utilizing the photocatalytic properties of nanoscale anatase at elevated temperatures (over 600 °C) the issue of phase stabilisation is of major interest. In this study, binary TiO₂/SiO₂ particles were synthesized by a flame aerosol process with TiCl₄ and SiCl₄ as precursors. The theoretical Si/Ti ratio was varied in the range of 0.7–1.3 mol/mol. The synthesized TiO₂/SiO₂ samples were heat treated at 900 and 1,000 °C for 3 h to determine the thermostability of anatase. Pyrogenic TiO₂ P25 (from Evonik/Degussa, Germany) widely applied as photocatalyst was used as non-thermostabilized reference material for comparison of photocatalytic activity of powders. Both the non-calcinated and calcinated powders were characterized by means of XRD, TEM and BET. Photocatalytic activity was examined with dichloroacetic acid (DCA) chosen as a model compound. It was found that SiO₂ stabilized the material retarding the collapse of catalyst surface area during calcination. The weighted anatase content of 85% remains completely unchanged even after calcination at 1,000 °C. The presence of SiO₂ layer/bridge as spacer between TiO₂ particles freezes the grain growth: the average crystallite size increased negligibly from 17 to 18 nm even during the calcination at 1,000 °C. Due to the stabilizing effect of SiO₂ the titania nanoparticles calcinated at 900 and 1,000 °C show significant photocatalytic activity. Furthermore, the increase in photocatalytic activity with calcination temperature indicates that the titania surface becomes more accessible either due to intensified cracking of the SiO₂ layer or due to enhanced transport of SiO₂ into the necks thus releasing additional titania surface.     

Transparent,photocatalytic, titania thin films formed at low temperature

A convenient method for the preparation of transparent, photocatalytic titania thin films is described. The films do not require annealing or thermal processing to develop photoactivity, thus can be applied to many thermally-sensitive substrates. Oxalic acid is used in place of the usual mineral acids to peptize the precipitated hydrous titania formed from the hydrolysis of titanium iso-propoxide. This leaves no inorganic residues in the film resulting in a higher quality film. The mineral phase and the photocatalytic activity produced are strongly influenced by the ratio of oxalic acid:titanium iso-propoxide employed. The peptization is carried out at 65 °C with vigorous stirring for 1 h in water containing 15% v/v ethanol, followed by a hydrothermal step at 95 °C. High oxalic acid:Ti molar ratios (0.5:1) result in rutile free sols, while lower ratios (0.25:1) result in anatase, rutile, brookite and TiO₂(B) in varying proportions. The films were exposed to low level UV light to cure, and photodecompose the residual organic components in the film. The photodecomposition of residual oxalic acid in the cast films were monitored using infrared spectroscopy. Photo-activity of the UV-cured films was compared by monitoring the decoloration of methylene blue stains on the film, by UV–Vis spectroscopy. Transmission was greater than 99% across the visible light region (400–800 nm).     

Photoactivity passivation of TiO<Subscript>2</Subscript> nanoparticles using molecular layer deposited (MLD) polymer films

Pigment-grade anatase TiO₂ particles (160 nm) were passivated using ultra-thin insulating films deposited by molecular layer deposition (MLD). Trimethylaluminum (TMA) and ethylene glycol (E.G) were used as aluminum alkoxide (alucone) precursors in the temperature range of 100–160 °C. The growth rate varied from 0.5 nm/cycle at 100 °C to 0.35 nm/cycle at 160 °C. Methylene blue oxidation tests indicated that the photoactivity of pigment-grade TiO₂ particles was quenched after 20 cycles of alucone MLD film, which was comparable to 70 cycles of Al₂O₃ film deposited by atomic layer deposition (ALD). Alucone films would decompose in the presence of water at room temperature and would form a more stable composite containing aluminum, which decreased the passivation effect on the photoactivity of TiO₂ particles.     

Biomimetic apatite induction on Ca-containing titania

To understand the apatite induction mechanism in SBF, Ca-containing titania film without CaTiO₃ phase was fabricated by micro-arc oxidation (MAO) at low voltage (230 V) in an electrolytic solution containing calcium acetate monohydrate. Macro-porous, Ca-containing titania film was formed on the titanium substrate and the oxidized layer was composed of anatase and rutile phase. When immersed in 1.5SBF, no apatite was induced in the MAO specimen similar to the CaTiO₃-containing titania. However, after hydrothermal treatment at 250 °C for 2 h, numerous precipitates, presumably calcium phosphates, were formed on the surface of the titania after 7 day immersion and titania surface was entirely covered with apatite after 14 days of immersion. This study clearly showed that Ca-containing titania has the capability to induce apatite in SBF and hydrothermal treatment plays a decisive role in apatite induction, particularly producing surface hydroxyl groups such as Ca–OH or Ti–OH.     

Effect of thermal annealing on the structure and microstructure of TiO2 thin films

Nanostructured TiO₂ thin films have been prepared through chemical route using sol-gel and spin coating techniques. The deposited films were annealed in the temperature range 400–1000°C for 1 h. The structure and microstructure of the annealed films were characterized by GAXRD, micro-Raman spectroscopy and AFM. The as-deposited TiO₂ thin films are found to be amorphous. Micro-Raman and GAXRD results confirm the presence of the anatase phase and absence of the rutile phase for films annealed up to 700°C. The diffraction pattern of the film annealed at 800 to 1000°C contains peaks of both anatase and rutile reflections. The intensity of all peaks in micro-Raman and GAXRD patterns increased and their width (FWHM) decreased with increasing annealing temperature, demonstrating the improvement in the crystallinity of the annealed films. Phase transformation at higher annealing temperature involves a competition among three events such as: grain growth of anatase phase, conversion of anatase to rutile and grain growth of rutile phase. AFM image of the asdeposited films and annealed films indicated exponential grain growth at higher temperature.      

Effect of calcination temperature on porous titania prepared from industrial titanyl sulfate solution

Porous titania with anatase phase was prepared via thermal hydrolysis of industrial titanyl sulfate solution, and subsequent calcination at different temperature. The as-prepared powders were characterized by TG, DSC, XRD, particle size distribution test, N₂ adsorption-desorption isotherm and SEM. Raising calcination temperature could accelerate the crystal growth, enlarge its specific surface area, pore diameter, and improve its photocatalytic activity. While too high temperature could destroy the pore structure even collapse. The optimal calcination temperature is 550 °C, and the obtained sample showed good thermal stability and high photocatalytic activity, with specific surface area of 189.3 m²/g and higher degree of crystallinity, and its photocatalytic degradation rate of methylene blue was of 95.76%.     

Highly frequency-, temperature-, and bias-stable dielectric properties of 500 °C processed Bi2SiO5 thin films with low dielectric loss

Excellent dielectric frequency, bias, and temperature stability of bismuth silicate (Bi₂SiO₅, BSO) thin films with a low dielectric loss has been obtained in this study. The thin films were prepared on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method at a relatively low annealing temperature of 500 °C. The BSO films have a preferred growth along (200) orientation with dense fine-grained surface morphology. The dielectric constant and dielectric loss of the thin film annealed at 500 °C are 57 and 0.01, respectively, at 100 kHz, with little change between 1 kHz and 100 kHz and in the bias electric field range between −250 kV/cm and 250 kV/cm, indicating that the thin film exhibits a low dielectric loss as well as excellent frequency and bias field stability. The dielectric-temperature measurements confirmed that the BSO thin film annealed at 500 °C also has good temperature stability between 150 K and 450 K. Our results suggest that the BSO thin films have potential applications in the next-generation integrated capacitors.     

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.     

The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity

Nanoparticle TiO₂/Ti films were prepared by a sol–gel process using Ti(OBu)₄ as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO₂ nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700 °C. TiO₂ nanoparticles calcined at 600 °C had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO₂ particles. Thus, the conclusion that 600 °C might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO₂/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO₂ nanoparticles, the adhesion of nanoparticle TiO₂ film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO₂/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO₂/Ti(3) film calcined at 600 °C as the chemical state of Ti⁴⁺, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260 nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO₂/Ti film with three layers calcined at 600 °C was the highest.     

Synthesis, characterization and photodegradation study of mixed-phase titania hollow submicrospheres with rough surface

Titania hollow submicrospheres with mixed phase (anatase-brookite or anatase-rutile) were synthesized via the combination of hydrothermal treatment and calcination of submicrospheres consisting of a polystyrene core and an amorphous TiO₂ shell. After hydrothermal treatment, amorphous titania shell could be transformed to anatase-brookite shell consisting of loose packed titania nanocrystals, which could be further converted to anatase-brookite (below 700 °C) or anatase-rutile titania (700-800 °C) hollow spheres with rough surface via calcination. The loose packing of titania nanocrystals not only inhibited the transformation temperature from anatase to rutile, but also provided titania hollow submicrospheres with high photodegradation activity of Rhodamine B. The photocatalytic activity of titania hollow spheres increased firstly then decreased when the calcination temperature was varied in the range of 450-800 °C, while hollow spheres obtained via calcinating at 700 °C exhibited the highest photocatalytic activity, which was five times higher than that of counterpart without hydrothermal treatment.     

Properties of mesoporous tungstosilicic acid/titania composites prepared by sol-gel method

The tungstosilicic acid/titania composites were prepared by the sol-gel method. Titanium isopropoxide was used as titania precursor, and urea as a low-cost template. The tungstosilicic acid (TSA) was added in the same step as that in which titania hydrogel is formed. The TSA-modified samples only showed the characteristic peaks of anatase phase of titanium oxide in the XRD patterns, indicating that the presence of TSA retarded the crystallization of the anatase phase and its transformation into the rutile phase. Spherical particles with sizes between 200 and 700 nm, formed by aggregation of nanoparticle aggregates (4-50 nm in size), were observed. The particle size increased when the TSA content was raised and also increased slightly with the thermal treatment temperature. Mesoporous materials were obtained, with a mean pore diameter higher than 3.1 nm. Both the increase of the TSA concentration in the solid and the calcination temperature led to a decrease in the specific surface area of the samples. The main heteropolyoxometallate species present in the composites is the [SiW₁₂O₄₀]⁴⁻ anion for the composites calcined up to 500 °C. The band gap energy decreased as a result of the introduction of TSA into the titania matrix, though it remained almost constant with the calcination temperature increase.     

Preparation of cadmium stannate films by spray pyrolysis technique

Cadmium stannate thin films were prepared by spray pyrolysis technique using cadmium acetate and tin(II) chloride precursors at substrate temperatures 450 °C and 500 °C. XRD pattern confirms the formation of orthorhombic (1 1 1) cadmium stannate phase for the film prepared at substrate temperature of 500 °C, whereas, films prepared at 450 °C are amorphous. Film formation does not occur at substrate temperature from 300 to 375 °C. SEM images reveal that the surface of the prepared Cd₂SnO₄ film is smooth. The average optical transmittance of ∼86% is obtained for the film prepared at substrate temperature of 500 °C with the film thickness of 400 nm. The optical band gap value of the films varies from 2.7 to 2.94 eV. The film prepared at 500 °C shows a minimum resistivity of 35.6 × 10⁻⁴ Ω cm.     

Photoluminescence characteristics of ZnGa2O4 thin films prepared by chemical solution method

Zinc gallate (ZnGa₂O₄) thin film phosphors have been formed on ITO glass substrates by a chemical solution method with starting materials of zinc acetate dihydrate, gallium nitrate hydrate and 2-methoxiethanol as a solution. The thin films were firstly dried at 100 °C and fired at 500 °C for 30 min and then, annealed at 500 °C and 600 °C for 30 min under an annealing atmosphere of 3% H₂/Ar. XRD patterns of the thin film phosphors showed (311) and (220) peak indicating ZnGa₂O₄ crystalline phase in which all the (311) peaks of the film phosphors synthesized on ITO glass and soda-lime glass revealed high intensity with increasing annealing temperature from 500 °C to 600 °C. The ZnGa₂O₄ thin film phosphors represented marked change in AFM surface morphologies according to an annealing temperature under an annealing atmosphere (3% H2/Ar). The film phosphor, annealed at 600 °C, showed the embossed pattern with relatively regular spacing in AFM surface morphology. The ZnGa₂O₄ thin film phosphors formed on ITO glass, which were annealed at different temperatures and showed distinctive spectra with peak wavelengths of 434 nm and 436 nm in the blue emission region.     

Temperature-resolved synchrotron X-ray diffraction of nanocrystalline titania in solvent: the effect of Cr–Sb and V–Sb doping

Nanocrystalline titania pigments were produced by high temperature-forced hydrolysis in a coordinating high-boiling solvent (and water for reference). The effect of synthesis conditions and co-doping with Cr–Sb and V–Sb on particle size and anatase-to-rutile transformation (A → R) was studied by temperature-resolved synchrotron X-ray diffraction. The experiments were performed directly on low concentration (3.5 vol.%) as-synthesized suspensions of titania nanoparticles (up to 230 °C) and on the corresponding dried powders (up to 950 °C). Crystallite size of as-synthesized nano-anatase is around 20 nm (glycol) or 70 nm (water); it exhibits a slow growth rate up to the onset temperature of the A → R. Phase composition and crystallite size are drastically influenced by both synthesis conditions and doping. Synthesis in water resulted in the simultaneous occurrence of anatase and brookite; transformation into rutile begins early but with a slower rate with respect to glycol-based samples. Doping affected the A → R, whose onset temperature in undoped titania (700 °C) was lowered to 650 °C (V–Sb) or prevented up to 950 °C (Cr–Sb). Both (V–Sb) and (Cr–Sb) dopings reduced the volume thermal expansion rate of anatase.     

Preparation of F-doped titania nanoparticles with a highly thermally stable anatase phase by alcoholysis of TiCl4

Pure anatase is a metastable phase and inclined to (transform) be transformed into rutile structure under heating over than 500 °C, which limits its suitability for high-temperature applications. Hitherto much research efforts have been made to increase the stability temperature of anatase structure. However, metallic doping usually introduced metallic oxides into titania at high temperature, and many nonmetallic doping are not competent for increasing the stability temperature of anatase structure up to 900 °C. In this study, F-doped anatase TiO₂ nanoparticles were conveniently prepared via the alcoholysis of TiCl₄ and the as-prepared product shows very high stability temperature up to 1000 °C before being transformed into rutile structure phase. On the basis of XPS results of F-doped titania annealed at different temperature, it is learned that the F atoms were anchored on the crystal planes of anatase in favor of decreasing the energy faces of anatase and stabilizing the anatase structure till annealed at 1300 °C all the anatase were transformed into rutile phase.     

Low-temperature synthesis of nanocrystalline β-dicalcium silicate with high specific surface area

β-Dicalcium silicate (β-Ca₂SiO₄) was synthesized for the first time by a simple solution combustion method using citric acid as fuel. The influence of calcination temperature on the average crystallite size, specific surface area and morphology of the powders were investigated by X-ray diffraction technique (XRD), scanning electron microscopy (SEM) and N₂ adsorption measurements (BET). The results showed that the increase of calcination temperature from 650°C to 1100°C resulted in larger crystallite size and lower specific surface area of β-Ca₂SiO₄. The highest specific surface area could reach as high as 26.7 m²/g when the as-burnt powders were calcined at 650°C.     

Effect of hydrothermal temperature on photocatalytic properties of TiO2 nanotubes

This work presents a study on the effect of hydrothermal temperature and structure on the photocatalytic activity of TiO₂ nanotubes (TNT) prepared using commercially available TiO₂ nanoparticles (P25). From the results, it was found that a higher hydrothermal temperature led to an increase in the specific surface area, total pore volume, and the size of mesopores in TNT. Moreover, the TNTs synthesized by the hydrothermal method had a new structure, which was very different from the anatase and rutile structures found in P25. The TNTs synthesized at 150 °C had the highest specific surface area of 371 m²/g. However, the TNTs synthesized at 180 °C exhibited the best photocatalytic efficiency and dye adsorption capacity, as compared to other TNTs, resulting from their well-developed mesopores.     

A spectroscopic ellipsometry study of TiO2 thin films prepared by ion-assisted electron-beam evaporation

Film characterization based on variable-angle spectroscopic ellipsometry (VASE) is desirable in order to understand physical and optical characteristics of thin films. A number of TiO₂ film samples were prepared by ion-assisted electron-beam evaporation with 200-nm nominal thickness, 2.0 Å/s deposition rate and 8 sccm oxygen flow rate. The samples were maintained at 250 °C during the deposition, and annealed in air atmosphere afterwards. As-deposited and annealed films were analyzed by VASE, spectrophotoscopy and X-ray diffractometry. From ellipsometry modeling process, the triple-layer physical model and the Cody–Lorentz dispersion model offer the best results. The as-deposited films are inhomogeneous, with luminous transmittance and band gap of 62.37% and 2.95 eV. The 300 °C and 500 °C are transition temperatures toward anatase and rutile phases, respectively. Increasing temperature results in an increase of refractive index, transmittance percentage and band gap energy. At 500 °C, the highest refractive index and band gap energy are obtained at 2.62 and 3.26 eV, respectively. The developed VASE-modeling process should be able to characterize other TiO₂ films, using similar physical and optical modeling considerations.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

Structural and electrochemical studies on thin film LiNi0.8Co0.2O2 by PLD for micro battery

Thin film of LiNi_0.8Co_0.2O₂ (LNCO) has been prepared by Pulsed Laser Deposition (PLD) technique at various post annealing temperatures. XRD results of LNCO thin film deposited on both Pt and Si substrates reveal relatively good crystalline nature at 500 °C which is in good agreement with the electrochemical results. ICP-AES composition analysis indicates 10 to 5% Li loss in the post annealed (400–700 °C) LNCO/Pt thin films; however the as prepared LNCO/Pt films show 17% excess of Li which are comparable with the LNCO target results. SEM analysis indicates phase separation at 600 °C and porous nature at 700–800 °C for LNCO/Pt films. Cyclic voltammetry (CV) scans of LiNi_0.8Co_0.2O₂ film post annealed at 500 °C show a pair of main cathodic and anodic peaks at 3.64 and 3.4 V, respectively with a narrow peak separation reveals good stability upon cycling. Whereas the LNCO films annealed at 600 °C and 700 °C indicate an additional anodic peak at lower potential besides a pair of major peaks which may be due to the phase separated morphology as evidenced from SEM analysis. Based on the structural and electrochemical results, a lithium-ion micro cell has been constructed with LNCO/Li_3.4V_0.6Si_0.4O₄(LVSO)/SnO configuration with the thickness of 1.535 µm and its electrochemical properties have been studied.