Electrical properties of polycrystalline TiO<Subscript>2</Subscript>: Equilibration kinetics

The equilibration kinetics was determined for high purity polycrystalline TiO₂ in the temperature range of 1,123–1,323 K, within a wide range of oxygen activity, . The equilibration kinetics experiments were performed within narrow p(O₂) ranges. The obtained kinetic data were used for the determination of the chemical diffusion coefficient, D _chem, which exhibits a complex dependence of p(O₂). The D _chem data are considered in terms of the effect of defect disorder on the mass transport kinetics in the chemical potential gradient. The reported diffusion data may be used for prediction of optimized processing conditions required to impose a homogeneous distribution of oxygen activity within the TiO₂ specimen. This project was performed as part of University of New South Wales R&D program on solar hydrogen.     

Half-metallicity in Rh-doped TiO<Subscript>2</Subscript> from ab initio calculations

First-principles calculations based on density functional theory (DFT) are performed to study the electronic structures and magnetic properties of Rh-doped TiO₂ crystals. The hybridization between Rh-4d and O-2p results in Rh becoming ferromagnetic with a magnetic moment of about 1.0 μ _B per supercell. The Rh-doped TiO₂ system exhibits half-metallic ferromagnetism based both DFT and DFT + U. The strong ferromagnetic couplings between local magnetic moments can be attributed to both the p-d hybridization and double-exchange mechanisms, as well as superexchange interaction. These results suggest an alternative approach to achieve promising dilute magnetic semiconductors by doping non-magnetic transition metals in a TiO₂ host.     

Heterogeneous Photocatalytic Oxidation of Pollutants in Air on TiO<Subscript>2</Subscript> Particles

A semiempirical method has been developed for analyzing the mechanism of heterogeneous reactions based on the Langmuir–Hinshelwood kinetic model modified using the first- order double-exponential decay approach. The method proved useful for describing the kinetics of photocatalytic oxidation (PCO) on TiO₂ particles in air for a wide range of substances: ketones, organophosphorus compounds, alkyl sulfides, and chlorinated hydrocarbons. The range of substances can certainly be considerably expanded. An equation of implicit function was derived that describes the kinetics of heterogeneous PCO of the zeroth, first, and intermediate (between the zeroth and first) orders. Approximation of the experimental time dependence of concentration using this equation makes it possible to determine the reaction order including the intermediate one, the characteristic decay time of the substance, and the fraction of the exponential components in the kinetic equation. This semiempirical method was used for processing both the original experimental data obtained in the present study and the literature data. The time dependences of trichloroethylene (TCE) concentrations in a closed space during the heterogeneous PCO on TiO₂ aerosol catalyst particles were studied using a specially designed unit. The catalytic activity increased with the aerosol concentration C _as : at C _as = 10.23, 14.17, and 19.85 g/m³, 90% purification of air from TCE was reached in 8.5, 5.0, and 1.5 min, respectively.     

Antibacterial effect of silver modified TiO<Subscript>2</Subscript>/PECVD films

This paper deals with photocatalytic activity of silver treated TiO₂ films. The TiO₂ films were deposited on glass substrates by plasma enhanced chemical vapor deposition (PECVD) in a vacuum reactor with radio frequency (RF) low temperature plasma discharge in the mixture of oxygen and titanium isopropoxide vapors (TTIP). The depositions were performed under different deposition conditions. Subsequently, the surface of TiO₂ films was modified by deposition of silver nanoparticles. Photocatalytic activity of both silver modified and unmodified TiO₂ films was determined by decomposition of the model organic matter (acid orange 7). Selected TiO₂ samples were used for tests of antibacterial activity. These tests were performed on Gram-negative bacteria Escherichia coli. The results clearly proved that presence of silver clusters resulted in enhancement of the photocatalytic activity, which was up to four times higher than that for pure TiO₂ films.     

Hierarchical structured ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>@RGO@TiO<Subscript>2</Subscript> composite as powerful visible light catalyst for degradation of fulvic acid

Hierarchical structured ZnFe₂O₄@reduced graphite oxide@TiO₂ (ZnFe₂O₄@RGO@TiO₂) nanocomposite was prepared by an electrostatic layer-by-layer route, which played a synthetic effect of Fenton oxidation of ZnFe₂O₄ and photocatalytic oxidation of TiO₂ to degrade fulvic acid (FA) solution under visible-light irradiation. In this method, RGO, as the middle layer, can effectively promote the photo-induced electron flow between the ZnFe₂O₄ and TiO₂ and further improve the efficiency of the photo-Fenton oxidation. The influencing factors on photo-Fenton oxidation, including solution pH, catalyst, and H₂O₂ dosage, have also been investigated. The results illustrated that the ternary composite presented the enhanced catalytic performance. Under visible light irradiation, the degradation efficiency of the sample on the FA solution can reach 95.4% within 3 h. In addition, the catalyst exhibited superior stability and reusability, and its degradation efficiency was still up to 90% after 5 cycles. Therefore, the composite will be a kind of efficient photocatalyst and had a promising application for visible-light driven destruction of organic pollutants.     

Correlation between the dynamics of oxygen atoms and oxidation kinetics of solid solutions based on Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CaCu<Subscript>2</Subscript>O<Subscript>8</Subscript>

The oxidation kinetics of Bi_1.3Pb_0.8Sr₂Ca_0.8Y_0.2Cu₂O_8+δ solid solutions at different temperatures and \(p_{O_2 } = 0.21\) atm is investigated by thermogravimetry. The results obtained are compared with the previously studied oxidation kinetics of Bi_1.3Pb_0.8Sr₂Ca_0.8Y_0.2Cu₂O_8+δ solid solutions. It is found that the substitution of yttrium for calcium leads to an appreciable retardation of the initial oxidation stage associated with the oxygen diffusion. The phonon spectra of the solid solutions are examined using inelastic neutron scattering on a DIN-2PI direct-geometry spectrometer. The high-frequency (>50 meV) phonon densities of states for yttrium-containing and yttrium-free solid solutions are analyzed. The possible model is proposed for a correlation between the differences observed in the high-frequency phonon densities of states attributed to the vibrations of oxygen atoms and the differences in the oxidation kinetics of the solid solutions under consideration.     

Magnetic ordering in Dy<Subscript>1-x</Subscript>Ca<Subscript>x</Subscript>BaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> for x = 0.0 and 0.1

The crystal and magnetic structures of Dy_1-xCa_xBaCo₂O_5.5 for x = 0.0 and 0.1 have been studied by neutron powder diffraction and the crystal structures of both compounds were found to be best described in space group Pmmm with a a_p × 2a_p × 2a_p unit cells where a_p is the lattice parameter of the cubic perovskite unit cell. The a- and b-axes were found to decrease and increase abruptly between 315 and 350 K as the temperature increases and the unit cell volumes exhibit signs of excess thermal expansion in the temperature range from 260 to 315 K. Dy_0.9Ca_0.1BaCo₂O_5.5 orders antiferromagnetically for T ≤ 305 K into a G-type magnetic structure with a 2a_p × 2a_p × 2a_p magnetic unit cell. DyBaCo₂O_5.5 exhibits two magnetically ordered phases and a G-type magnetic structure was observed at the investigated temperatures 260 and 290 K. A 2a_p × 2a_p × 4a_p magnetic unit cell was needed for indexing of the magnetic reflections observed for T ≤ 230 K. The low temperature magnetic structure of DyBaCo₂O_5.5 is different from the observed magnetic structures of TbBaCo₂O_5.5 and HoBaCo₂O_5.5 despite the proximity of Tb, Dy and Ho in the periodic table. It is a relatively complex antiferromagnetic structure with both pyramidally and octahedrally coordinated Co ions in the intermediate spin state. It contains both ferro- and antiferromagnetic interactions and the magnetic moments are canted in the a, b-plane. The canting angles between the magnetic moments and the b-axis are 6.6 and 50.0° at 20 K for the pyramidally and octahedrally coordinated Co ions, respectively. The high and low temperature magnetic phases were found to coexist at 230 K.     

Fabrication and electrochemical investigation of Li<Subscript>0.5</Subscript>TiO<Subscript>2</Subscript> as anode materials for lithium ion batteries

Hexagonal and cubic Li_0.5TiO₂ particles have been fabricated through magnesiothermic reduction of Li₂TiO₃ particles in a temperature range of 600 to 640 °C. The prolonged reduction time results in lattice transition from hexagonal to cubic structure of Li_0.5TiO₂. Their microstructures, valance state, chemical composition, as well as electrochemical performance as anode candidates for lithium ion batteries have been characterized and evaluated. The hexagonal Li_0.5TiO₂ exhibits better electrochemical activity compared with the cubic one. Further, the carbon-coated hexagonal Li_0.5TiO₂ displays improved electrochemical performance with initial reversible capacity of 176.6 mAh g^?1 and excellent cyclic behavior except capacity fading in the initial 10 cycles, which demonstrate a novel anode candidate for long lifetime lithium ion batteries.     

EPR Monitoring of BaTiO<Subscript>3</Subscript> Formation

BaCO₃ and anatase-type TiO₂ were adopted as initial materials to prepare BaTiO₃ powder by the solid-state reaction method at a heating rate of 350°C/h. The electron paramagnetic resonance (EPR) technique was employed to monitor the formation of BaTiO₃. TiO₂ showed a series of complicated EPR signals associated primarily with Fe impurities. The formation of BaTiO₃ can be monitored in terms of the evolution of EPR signals associated with Fe impurities with calcination and measurement temperatures. The activation of the g = 2.004 signal above the Curie point of BaTiO₃ and the disappearance of the other EPR signals in the BaCO₃/TiO₂ mixture at room temperature are characteristic of the formation of BaTiO₃.     

Sensitizing of Sm<Superscript>3+</Superscript> fluorescence by silver dopant in the TiO<Subscript>2</Subscript> films

Composite material based on a TiO₂ matrix doped with Sm³⁺ ions and co-doped with silver was investigated. Samarium ions together with nano- and micro-aggregates of silver were incorporated into the titanium alkoxide during the sol-gel process. Samarium ions were excited either directly (λ _exc = 488 nm) or through the TiO₂ host (λ _exc = 355 nm). It was revealed that samarium fluorescence (λ _exc = 488 nm) in gelled TiO₂ films is enhanced by up to 20 times in the vicinity of silver inclusions. Sensitizing and plasmonic mechanisms of enhancement in Sm³⁺ fluorescence are discussed.     

First-principles calculations on implanted TiO<Subscript>2</Subscript> by 3d transition metal ions

3d transition metal (V, Cr and Fe) ions are implanted into TiO₂ by the method of metal ion implantation. The electronic band structures of TiO₂ films doped 3d transition metal ions have been analyzed by ab initio band calculations based on a self-consistent full-potential linearized augmented plane-wave method within the first-principle formalism. Influence of implantation on TiO₂ films is examined by the method of UV-visible spectrometry. The results of experiment and calculation show that the optical band gap of TiO₂ films is narrowed by ion implantation. The calculation shows that the 3d state of V, Cr and Fe ions plays a significant role in red shift of UV-Vis absorbance spectrum.     

Glass-forming ability and thermal stability of Fe<Subscript>62</Subscript>Nb<Subscript>8−x</Subscript>Zr<Subscript>x</Subscript>B<Subscript>30</Subscript> and Fe<Subscript>72</Subscript>Zr<Subscript>8</Subscript>B<Subscript>20</Subscript> amorphous alloys?

Glass-forming ability (GFA) and thermal stability of Fe₆₂Nb₈B₃₀, Fe₆₂Nb₆Zr₂B₃₀ and Fe₇₂Zr₈B₂₀ at % amorphous alloys were investigated by calorimetric (DSC and DTA) measurements. The crystallization kinetics was studied by DSC in the mode of continuous versus linear heating and it was found that both the glass transition temperature, T _g , and the crystallization peak temperature, T _p , display strong dependence on the heating rate. The partial replacement of Nb by Zr leads to lower T _g and T _x temperatures and causes a decrease of the supercooled liquid region. JMA analysis of isothermal transformation data measured between T _g and T _x suggests that the crystallization of the Fe₆₂Nb₈B₃₀ and Fe₆₂Nb₆Zr₂B₃₀ amorphous alloys take place by three-dimensional growth with constant nucleation rate. Nb enhances the precipitation of the metastable Fe₂₃B₆ phase and stabilizes it up to the third crystallization stage. Zr addition increases the lattice constant of Fe₂₃B₆ and, at the same time, decreases the grain size.     

Photoaccumulating film systems based on TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript> and TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript>:V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanoheterostructures

The thin-film photocatalysts TiO₂/MoO₃ and TiO₂/MoO₃:V₂O₅ obtained by a combination of sol–gel and sintering techniques were studied using the photooxidation of probing dyes, EPR spectroscopy, X-ray diffraction analysis, and electron microscopy. It was shown that due to charge accumulation caused by UV irradiation, these photocatalysts retain their oxidative activity and ability for self-sterilization in the dark for a long time after irradiation was terminated (up to 5 h for TiO₂/MoO₃:V₂O₅).     

Reactivity at the oxygen/titania interface and the related charge transfer

The present paper reports the reactivity between TiO₂ and oxygen and the related charge transfer at 298 and 1,073 K. The studies were performed using work function measurements. It was found that oxidation of TiO₂ at 1,073 K and p(O₂) = 75 kPa, initially standardized at 1,173 K and p(O₂) = 10 Pa, results in work function changes that are consistent with the theoretical model of the charge transfer during oxygen chemisorption and oxygen incorporation at the absence of structural transitions. However, oxidation of TiO₂ at 298 K, p(O₂) = 75 kPa, which has been initially standardized at 1,173 K in extremely reducing conditions at p(O₂) = ∼10⁻¹⁰ Pa, results in work function changes that are consistent with low-dimensional structural changes of the surface layer. It is shown that oxidation of strongly reduced TiO₂ at 298 K results in a decrease of work function, which cannot be explained without assuming the structural changes of the outermost surface layer.     

Efficient carbon-doped nanostructured TiO<Subscript>2</Subscript> (anatase) film for photoelectrochemical solar cells

In this paper, we have demonstrated that carbon-doped nanostructured TiO₂ (CD ns-TiO₂) films could be prepared simply and cheaply with oxalic acid and tetrabutylammonium bromide (Bu₄N·Br) as the carbon sources. The surface morphology of the films was a multiple-porous network structure.The average size of nanoparticle was about 40 nm. Carbon doped into substitutional sites of TiO₂ has also proven to be indispensable for band-gap narrowing and photovoltaic effect. Carbon doping lowered the band gap of n-TiO₂ to 1.98, 1.64, and 1.26 eV. The CD ns-TiO₂ film was first used as photoanode for solar cells, exhibiting high photocurrent densities (l.34 mA/cm²) and yielding an overall conversion efficiency (η) of 4.42 %.     

Photocatalytic properties of nanocrystalline TiO<Subscript>2</Subscript> thin films doped with Tb

In this work photocatalytic properties of TiO₂ thin films doped with different amount of Tb have been described. Thin films were prepared by high energy reactive magnetron sputtering process. Comparable photocatalytic activity has been found for all doped TiO₂ thin films, while different amounts of Tb dopant (0.4 and 2.6 at. %) results in either an anatase or rutile structure. It was found that the terbium dopant incorporated into TiO₂ was also responsible for the amount of hydroxyl groups and water particles adsorbed on the thin film surfaces and thus photocatalytic activity was few times higher in comparison with results collected for undoped TiO₂ thin films.     

Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.     

Novel nanocomposite membranes based on polybenzimidazole and Fe<Subscript>2</Subscript>TiO<Subscript>5</Subscript> nanoparticles for proton exchange membrane fuel cells

In this work, Fe₂TiO₅ nanoparticles were used for improving the proton conductivity, and water and acid uptake of polybenzimidazole (PBI)-based proton exchange membranes. The nanocomposite membranes have been prepared using different amounts of Fe₂TiO₅ nanoparticles and dispersed into a PBI membrane with the solution-casting method. The prepared membranes were then physico-chemically and electrochemically characterized for use as electrolytes in high-temperature PEMFCs. The PBI/Fe₂TiO₅ membranes (PFT) showed a higher acid uptake and proton conductivity compared with the pure PBI membranes. The highest acid uptake (156 %) and proton conductivity (78 mS/cm at 180 °C) were observed for the PBI nanocomposite membranes containing 4 wt% of Fe₂TiO₅ nanoparticles (PFT₄). The PFT₄ composite membrane showed 380 mW/cm² power density and 760 mA/cm² current density in 0.5 V at 180 °C at dry condition. The above results indicated that the PFT₄ nanocomposite membranes could be utilized as proton exchange membranes for high-temperature fuel cells.     

Photoconductivity studies on amorphous and crystalline TiO<Subscript>2</Subscript> films doped with gold nanoparticles

In this work, amorphous and crystalline TiO₂ films were synthesized by the sol–gel process at room temperature. The TiO₂ films were doped with gold nanoparticles. The films were spin-coated on glass wafers. The crystalline samples were annealed at 100°C for 30 minutes and sintered at 520°C for 2 h. All films were characterized using X-ray diffraction, transmission electronic microscopy and UV-Vis absorption spectroscopy. Two crystalline phases, anatase and rutile, were formed in the matrix TiO₂ and TiO₂/Au. An absorption peak was located at 570 nm (amorphous) and 645 nm (anatase). Photoconductivity studies were performed on these films. The experimental data were fitted with straight lines at darkness and under illumination at 515 nm and 645 nm. This indicates an ohmic behavior. Crystalline TiO₂/Au films are more photoconductive than the amorphous ones.     

Influence of nanocrystalline structure and composition on hardness of thin films based on TiO<Subscript>2</Subscript>

In this work, the influence of Tb-doping on structure, and especially hardness of nanocrystalline TiO₂ thin films, has been described. Thin films were formed by a high-energy reactive magnetron sputtering process in a pure oxygen atmosphere. Undoped TiO₂-matrix and TiO₂:Tb (2 at. % and 2.6 at. %) thin films, had rutile structure with crystallite sizes below 10 nm. The high-energy process produces nanocrystalline, homogenous films with a dense and close packed structure, that were confirmed by X-ray diffraction patterns and micrographs from a scanning electron microscope. Investigation of thin film hardness was performed with the aid of a nanoindentation technique. Results of measurements have shown that the hardness of all manufactured nanocrystalline films is above 10 GPa. In the case of undoped TiO₂ matrix, the highest hardness value was obtained (14.3 GPa), while doping with terbium results in hardness decreasing down to 12.7 GPa and 10.8 GPa for TiO₂:(2 at. % Tb) and TiO₂:(2.6 at. % Tb) thin films, respectively. Incorporation of terbium into TiO₂-matrix also allows modification of the elastic properties of the films.