Remarkable catalytic activity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanocomposites prepared by hydrothermal method for the degradation of methyl orange

Visible light Bi₂O₃/TiO₂ nanocomposites are successfully prepared with different dosages of Bi₂O₃ by hydrothermal process. All the as-prepared samples are characterized by X-ray diffraction (XRD), scanning and transmission electron microscopes (SEM and TEM), Brunauer-Emmett-Teller analysis (BET), N₂ adsorption-desorption measurement, and UV-Vis diffuse reflectance spectra (DRS). XRD and Raman spectra reveal the anatase phase of both TiO₂ and Bi₂O₃/TiO₂ nanocomposites. X-ray diffraction patterns demonstrate that the bismuth ions did not enter into the lattice of TiO₂, and Bi₂O₃ is extremely dispersive on the surface of TiO₂ nanoparticles. The incorporation of Bi₂O₃ in TiO₂ leads to the spectral response of TiO₂ in the visible light region and efficient separation of charge carriers. The enhanced visible light activity is tested by the photocatalytic degradation of methyl orange under light illumination, and the performance of Bi₂O₃/TiO₂ nanocomposites are superior than that of pure TiO₂ which is ascribed to the efficient charge separation and transfer across the Bi₂O₃/TiO₂ junction. Bi₂O₃/TiO₂ nanocomposite (20 mg) loaded with 0.25 of Bi₂O₃ dispersed in 50 ml of 5 ppm methyl orange solution exhibited the highest photocatalytic activity of 98.86% within 240 min of irradiation, which is attributed to the low band gap, high surface area, and the strong interaction between Bi₂O₃ and TiO₂.     

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).     

Nanoparticles dispersion in processing functionalised PP/TiO<Subscript>2</Subscript> nanocomposites: distribution and properties

Future innovations in textiles and fibrous materials are likely to demand fibres with enhanced multifunctionality. The fibres can be functionalized by dispersing nanoadditives into the polymer during melt compounding/spinning. TiO₂ nanoparticles have the potential to improve UV resistance, antistatic, as well as impart self-cleaning by photocatalysis and thereby de-odour and antimicrobial effects. In this study, a micro-lab twin-screw extruder was used to produce samples of polypropylene (PP) nanocomposite monofilaments, doped with nano titanium oxide (TiO₂)/manganese oxide (MnO) compound having size ranging from 60 to 200 nm. As a control sample, PP filaments without additives were also extruded. Three samples were produced containing different concentrations (wt%) of the TiO₂ compound, i.e. 0.95, 1.24 and 1.79%. Nano metal-oxide distribution in the as-spun and drawn nanocomposite filaments was analysed. Although, there are small clusters of the nanoparticles, the characterizing techniques showed good dispersion and distribution of the modified TiO₂ along and across the processed filaments. From UV spectroscopy and TGA, a significant enhancement of polypropylene UV protection and thermal stability were observed: PP with higher percentage of TiO₂ absorbed UV wavelength of 387 nm and thermally decomposed at 320.16 °C accompanied by 95% weight loss.     

Impedance spectroscopy study of Na<Subscript>1/2</Subscript>Sm<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> ceramic

Complex impedance analysis of a valence-compensated perovskite ceramic oxide Na_1/2Sm_1/2TiO₃, prepared by a mixed oxide (solid-state reaction) method, has been carried out. The formation of single-phase material was confirmed by X-ray diffraction studies, and it was found to be an orthorhombic phase at room temperature. In a scanning electron microscope, grains separated by well-defined boundaries are visible, which is in good agreement with that of impedance analysis. Alternating current impedance measurements were made over a wide temperature range (31–400 °C) in an air atmosphere. Complex impedance and modulus plots helped to separate out the contributions of grain and grain boundaries to the overall polarization or electrical behavior. The physical structure of the samples was visualized most prominently at higher temperatures (275 °C) from the Nyquist plots showing inter- and intragranular impedance present in the material. The frequency dependence of electrical data is also analyzed in the framework of the conductivity and modulus formalisms. The bulk resistance, evaluated from the impedance spectrum, was observed to decrease with rise in temperature, showing a typical negative temperature coefficient of resistance-type behavior like that of semiconductors. The modulus mechanism indicates the non-Debye type of conductivity relaxation in the materials, which is supported by the impedance data. PACS 77.22.Ch; 77.22.Ej; 77.22.Gm; 77.22.Jp; 77.84.Bw     

Synthesis and nanostructural investigation of TiO<Subscript>2</Subscript> nanorods doped by SiO<Subscript>2</Subscript>

TiO₂ Nano rods can be used as dye-sensitized solar cells, various sensors and photocatalysts. These nanorods are synthesized by a hydrothermal corrosion process in NaOH solution at 200°C using TiO₂ powder as the source material. In the present work, the synthesis of TiO₂ nanorods in anatase, rutile and Ti₇O₁₃ phases and synthesis of TiO₂ nanorods by incorporating SiO₂ dopant, using the sol–gel method and alkaline corrosion are reported. The morphologies and crystal structures of the TiO₂ nanorods are characterized using field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) study. The obtained results show not only an aggregation structure at high calcination temperatures with spherical particles but also Ti–O–Si bonds having four-fold coordination with oxygen in SiO^4 −.     

Photogreying of TiO<Subscript>2</Subscript> nanoparticles

Photogreying, the change in brightness on UV irradiation in the absence of oxygen, of TiO₂ nanoparticulate dispersions is shown to depend on the nature of the liquid, consistent with a surface reaction. Measurements on a series of TiO₂ particles (mainly 75×10 nm) dispersed in, e.g., alkyl benzoate correlate well with those on the same TiO₂’s dispersed in a second liquid (e.g. propan-2-ol). Photogreying in propan-2-ol is paralleled by photocatalytic-oxidation activity, indicating a common origin – UV-generation of charge carriers. Further, photogreying parallels Ti³⁺ formation. Hence, although appearance and the visible spectra of photogreyed particles both differ from those of Ti³⁺ in ≤10 nm colloidal TiO₂, we suggest that photogreying is caused by capture of UV excited electrons to form Ti³⁺. Surface treatment reduces photogreying, and we speculate that differences between uncoated samples reflect differences in the number of potentially reducible Ti’s.     

Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Electrical properties of TiO<Subscript>2</Subscript>: equilibrium vs dynamic electrical conductivity

The present work reports semiconducting properties of high purity TiO₂ determined in the gas/solid equilibrium, as well as during controlled heating and cooling in the range 300–1,273 K. The activation energy of the electrical conductivity is considered in terms of the activation enthalpy of the formation of ionic defects and the activation enthalpy of the mobility of electronic defects. These data, determined from the dynamic electrical conductivity experiments, are compared to the electrical conductivity data determined in equilibrium. It is shown that only the equilibrium electrical conductivity data for high-purity TiO₂ are well defined. It is shown that the activation energy of the electrical conductivity determined in equilibrium differs substantially from that for the dynamic electrical conductivity data during cooling and heating. It is concluded that the formation enthalpy term determined from the dynamic conductivity data is determined by the heating/cooling rate rather than materials’ properties.     

Metal/TiO<Subscript>2</Subscript> interfaces for memristive switches

The interfaces between metal electrodes and the oxide in TiO₂-based memristive switches play a key role in the switching as well as in the I–V characteristics of the devices in different resistance states. We demonstrate here that the work function of the metal electrode has a surprisingly minor effect in determining the electronic barrier at the interface. In contrast, Ti oxides can be readily reduced by most electrode metals. The amount of oxygen vacancies created by these chemical reactions essentially determines the electronic barrier at the device interfaces.     

Optical and electrical properties of nanocrystalline TiO<Subscript>2</Subscript>:Pd semiconducting oxides

Electrical and optical properties of TiO₂:Pd thin films deposited from Ti-Pd mosaic targets sputtered in reactive oxygen plasma have been studied. The properties were investigated for thin films with the Pd amount of 5.5 at. %, 8.4 at. % and 23 at. %. Based on resistivity measurements a drop from 10³ down to almost 10⁻³Ωcm has been recorded when the Pd amount was varied from 5.5 at. % to 23 at. %, respectively. Moreover, it was shown that doping with different amounts of Pd results in the possibility of obtaining both types of electrical conduction: n-type for the TiO₂ with 5.5 at. % and 8.4 at. % of Pd and p-type for the TiO₂ with 23 at. % of Pd thin films. From optical measurements it has been found that as the Pd amount was increased the transmission through the thin films was reduced and position of the fundamental absorption edge was shifted toward a longer wavelength range of up to 600 nm. The optical band gap was calculated for direct and indirect transitions from optical absorption spectra. Structural properties were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD patterns displayed occurrence of the crystalline, TiO₂-rutile for lower Pd amounts (5.5 at. %, 8.4 at. %), while the TiO₂:Pd (23 at. %) thin films displayed XRD-amorphous behaviour. Images obtained from AFM displayed dense, nanocrystalline structure with homogenous distribution of crystallites. Additionally performed secondary ion mass spectroscopy investigation confirmed homogenous distribution of Pd in the whole thickness of the prepared thin films.     

Assembly,characterization, and photocatalytic activities of TiO<Subscript>2</Subscript> nanotubes/CdS quantum dots nanocomposites

The semiconductor quantum dots (QDs) can be very efficient to tune the response of photocatalyst of TiO₂ to visible light. In this study, CdS QDs formed in situ with about 8 nm have been successfully deposited onto the surfaces of TiO₂ nanotubes (TNTs) to form TNTs/CdS QDs nanocomposites by use of a simple bifunctional organic linker, thiolactic acid. The diffuse reflectance spectroscopy (DRS) spectra of as prepared samples showed that the absorption edge of the TNTs/CdS composite is extended to visible range, with absorption edge at 530 nm. The photocatalytic activity and stability of TNTs/CdS were also evaluated for the photodegradation of rhodamine B. The results showed that when TNTs/CdS QDs was used, photocatalytic degradation of RhB under visible light irradiation reached 91.6%, higher than 45.4 and 30.5% for P25 and TNTs, respectively. This study indicated that the TNTs/CdS QDs nanocomposites were superior catalysts for photodegradation under visible light irradiation compared with TNTs and P25 samples, which may find wide application as a powerful photocatalyst in environmental field.     

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.     

The effect of anodising time on the electrochemical behaviour of the Ti/TiO<Subscript>2</Subscript> NTs/IrO<Subscript>2</Subscript>-RuO<Subscript>2</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> anode

Nowadays, mixed metal oxide (MMO) anodes are a superior alternative to lead alloys in electrowinning processes. Passivation of titanium substrate is the most common mechanism of deactivation in these anodes. In this research, titanium oxide nanotubes have been utilised as an interlayer between the substrate and a mixed metal oxide coating in order to improve the anode electrochemical behaviour and life via retardation of titanium passivation. Anodising of the substrate was done in 0.5 wt% hydrofluoric acid for 30, 60 and 240 min. The samples were subsequently coated with a coating composed of IrO₂-RuO₂-Ta₂O₅. The microstructure of different samples was observed by scanning with an electron microscope, and the electrochemical behaviour of the samples was studied by accelerated life test, cyclic voltammetry and electrochemical impedance spectroscopy. The studies showed that formation of titanium oxide nanotubes with anodising times of 60 and 240 min increases the life of the anode through the provision of a compact coating. The life of the anode which was anodised for 240 min lasted about 20% longer than the sample which had a substrate without any anodised layer.     

Preparation and electrocatalytic performance of the Pt supported on the alkali-treated nanoporous TiO<Subscript>2</Subscript> material

In this work, we prepared a Pt/TiO₂ electrocatalyst for methanol electrooxidation. The Pt nanoparticles were loaded on the alkali-treated nanoporous TiO₂ by a convenient deposition method. The morphology of the nanoporous TiO₂ was depended on the alkali treatment time. After 15-min alkali treatment, the flocculent-liked nanostructure was formed, and the specific surface area of the material was the largest. The amounts as well as the size and distribution of Pt nanoparticles were controlled by loading times. The catalytic activities of the catalysts toward methanol electrooxidation were tested in the alkaline condition. The alkali treatment time and chemical loading time were the key factors that influenced the catalytic activities. The optimal catalytic activity was achieved when the loading time was six.     

Synthesis,characterization, and thermal stability of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript>/CR-Ag multilayered nanostructures

The controllable synthesis and characterization of novel thermally stable silver-based particles are described. The experimental approach involves the design of thermally stable nanostructures by the deposition of an interfacial thick, active titania layer between the primary substrate (SiO₂ particles) and the metal nanoparticles (Ag NPs), as well as the doping of Ag nanoparticles with an organic molecule (Congo Red, CR). The nanostructured particles were composed of a 330-nm silica core capped by a granular titania layer (10 to 13 nm in thickness), along with monodisperse 5 to 30 nm CR-Ag NPs deposited on top. The titania-coated support (SiO₂/TiO₂ particles) was shown to be chemically and thermally stable and promoted the nucleation and anchoring of CR-Ag NPs, which prevented the sintering of CR-Ag NPs when the structure was exposed to high temperatures. The thermal stability of the silver composites was examined by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). Larger than 10 nm CR-Ag NPs were thermally stable up to 300 °C. Such temperature was high enough to destabilize the CR-Ag NPs due to the melting point of the CR. On the other hand, smaller than 10 nm Ag NPs were stable at temperatures up to 500 °C because of the strong metal-metal oxide binding energy. Energy dispersion X-ray spectroscopy (EDS) was carried out to qualitatively analyze the chemical stability of the structure at different temperatures which confirmed the stability of the structure and the existence of silver NPs at temperatures up to 500 °C.     

Study of the anisotropy of the dielectric response of Na<Subscript>1/2</Subscript>Bi<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectric

The dielectric response, conductivity, and domain structure of (Na_1/2Bi_1/2)TiO₃ single crystals are studied in the temperature range of 290–750 K for the [100], [110], and [111] crystallographic directions. It is shown that the region of optical isotropization is observed in polarized light in the temperature range of 570–620 K. In this case, the birefringence (Δn) decreases and disappears (together with the image of the domain structure) for the [100] directions. The region of optical isotropization in the [111] directions is characterized by the disappearance of the image of the domain structure and by the existence of individual regions with partial quenching. The domain structure in the [110] directions remains distinguished against the background of a significant decrease in Δn in the indicated temperature range. The region of isotropization is also manifested in the temperature dependence of the imaginary part of the dielectric response and is determined by the isotropic character of the conductivity in the range of 570–620 K. The bulk conductivity has a thermally activated character with activation energies E _a = 50?60 meV at T < 500 K and E _a = 700?900 meV for T > 620 K. The low-frequency dispersion of the dielectric response is determined by the Maxwell–Wagner mechanism and is due to an increase in the ionic conductivity at temperatures above 620 K. The anisotropy of the susceptibility holds in the entire studied ranges of frequencies (25 Hz–1 MHz) and temperatures.