Substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of perovskite-structured Ba(In0.5Ta0.5−xBix)O3 semiconductors

We have investigated the substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of barium indium tantalate. X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that, under oxygen atmosphere of 1 atm, pentavalent Bi ions are successfully stabilized in the octahedral site of the perovskite tantalate lattice. According to diffuse reflectance UV-vis spectroscopic analysis, the Bi substitution gives rise to the significant narrowing of band gap of barium indium tantalate even at a low Bi content of ∼5%, underscoring a high efficiency of Bi substitution in the band gap engineering. Such an effective narrowing of the band gap upon the Bi substitution would be attributable to the lowering of conduction band position due to the high electronegativity of Bi^V substituent. As a result of band gap engineering, the Ba(In_0.5Ta_0.5−xBi_x)O₃ compounds with x ≥ 0.03 can generate photocurrents under visible light irradiation (λ > 420 nm). Based on the present experimental findings, it becomes clear that the substitution of highly electronegative p-block element like Bi^V ion can provide a very powerful tool for tailoring the electronic structure and physicochemical properties of wide band gap semiconductors.     

Solvothermal synthesis of nanorods of ZnO, N-doped ZnO and CdO

ZnO nanorods with diameters in the 80-800 nm range are readily synthesized by the reaction of zinc acetate, ethanol and ethylenediamine under solvothermal conditions. The best products are obtained at 330 °C with a slow heating rate. Addition of the surfactant Triton^®-X 100 gave nanorods of uniform (300 nm) diameter. By adding a small amount of liquid NH₃ to the reaction mixture, N-doped ZnO nanorods, with distinct spectroscopic features are obtained. CdO nanorods of 80 nm diameter have been prepared under solvothermal conditions using a mixture of cadmium cupferronate, ethylenediamine and ethanol at 330 °C. Similarly, Zn_1−xCd_xO nanorods of a 70 nm diameter are obtained under solvothermal conditions starting with a mixture of zinc acetate, cadmium cupferronate, ethanol and ethylenediamine.     

Shape-controlled synthesis of manganese oxide nanoplates by a polyol-based precursor route

Manganese oxide nanoplates with different shapes have been prepared based on an ethylene glycol-mediated route. The first step consists of precipitating manganese alkoxide precursor in a polyol process from the reaction of manganese acetate with ethylene glycol. During this process, the morphologies of the prepared precursor could be tuned from disc-shaped to hexagonal nanoplates by introducing different organic additives. The second step involves the treatment of the precursor under different conditions. Crystalline Mn₂O₃ with the same morphology was readily obtained by calcination of the manganese alkoxide precursor. Furthermore, Mn₃O₄ nanoplates could be obtained by immersing the precursor into the deionized water.     

Photoelectrochemical and physical properties of tungsten trioxide films obtained by aerosol pyrolysis

Aerosol pyrolysis (AP) was used for preparing semiconducting films of tungsten trioxide using peroxotungstic acid as a precursor. The films were characterized by SEM, XRD, and by their photoelectrochemical response. Porous, polycrystalline (monoclinic) films of thickness up to 3 μm were prepared. An incident photon to current efficiency (IPCE) of 0.55 at 365 nm was obtained for films of 1 μm thickness on conducting F:SnO₂/glass substrates under depletion conditions, in junctions with aqueous electrolytes. The spectral (photocurrent) response extended into the visible region (up to 470 nm) which is of importance for solar applications like photocatalysis.     

Neutron diffraction study of the oxychloride layered perovskite, (CuCl)LaNb2O7

The structure of the oxychloride layered perovskite, (CuCl)LaNb₂O₇, has been examined by neutron diffraction. Rietveld refinement of room temperature neutron TOF data, while consistent with the previous X-ray study, allows for an improved modeling of the structure. The structure consists of double perovskite layers (LaNb₂O₇) separated by copper chloride layers. The copper is octahedrally coordinated, bridging between apical oxygens from the perovskite layer and surrounded by four chlorines in the CuCl plane; this gives rise to edge-sharing CuO₂Cl₄ octahedra. The chlorines within the CuCl plane were found to move off the ideal (0, 0, 1/2) position to a more general position, (x, 0, 1/2). This disorder leads to a combination of four short and two long distances, common to the Jahn-Teller distorted environments for d⁹ copper. Structural details are discussed with respect to their influence on the chlorine disorder.     

Photoluminescence and low-voltage cathodoluminescence characteristics of blue phosphor, ZnGa2O4:M (M = Na, Ag)

Photoluminescence and low-voltage cathodoluminescence characteristics of ZnGa₂O₄ phosphor doped with monovalent ions has been studied. Monovalent ions such as Na⁺ and Ag⁺ are incorporated into ZnGa₂O₄ lattices in order to increase the concentration of oxygen vacancies in the spinel lattice. By doping low concentrations of monovalent ions (Na⁺, Ag⁺) into ZnGa₂O₄, the self-activated blue luminescence originated from oxygen vacancies is enhanced. Also, the blue luminescence intensity is enhanced more along with a good color purity by annealing ZnGa₂O₄:Na⁺ in a reducing atmosphere, which is due to increasing the concentration of oxygen vacancies even more. The luminescence band at the UV region (λ_max=360 nm) does not become the major luminescence band by introducing Na⁺ ion into the ZnGa₂O₄ lattice, while the UV luminescence band becomes the major one by annealing the undoped ZnGa₂O₄ in a reducing atmosphere.     

Influence of thermal treatment conditions on two-dimensional crystal growth of nanocrystal corundum abrasives

The effect of thermal treatment on mechanical property and microstructure evolution in two-dimension of nanocrystal corundum abrasives has been investigated. The abrasives with and without presence of bond were calcined at different thermal treatment temperatures. The results indicated that thermal treatment conditions had obvious influence on crystal size and mechanical strength of corundum abrasives. Crystal size increased with increasing of the calcining temperature, and crystal growth of sample with presence of bond was more remarkable than that without presence of bond. And it was found that 950 °C is the critical temperature of abnormal crystal growth of corundum abrasives in the heated treatment conditions. Beyond this critical temperature, crystal size evidently increased while strength and wear resistance of abrasive decreased. In this case, the degradation of the abrasive in microstructure and strength should be important considerations for the preparation of ceramic corundum abrasive grinding tool.     

Low temperature synthesis and characterization of strontium stannate–titanate ceramics

A novel modified chimie douce synthetic approach based on the gel to crystallite conversion (G–C) method has been developed to prepare strontium titanate SrTiO₃, strontium stannate SrSnO₃, and mixed strontium stannate–titanate SrSn_1−xTi_xO₃ (x = 0.05–0.5). The obtained materials were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The formation of fully crystalline SrTiO₃ was observed in the temperature range of 800–1000 °C. The formation of monophasic SrSnO₃ occurs in the temperature range of 700–900 °C. At lower and higher temperatures the formation an impurity phases such as SrCO₃ and SnO₂ takes place. The same synthetic approach has been applied for the preparation of mixed strontium stannates–titanates SrSn_1−xTi_xO₃. The SEM images of SrTiO₃ samples indicated that the powder particles are 1–5 μm in size having approximately plate-like shape. Quite different surface morphology was determined for SrSnO₃ samples revealing the size of crystals from 500 nm to 40 μm. For the composition with x = 0.15, it was observed that the grain growth is uniform and the size of the grains is of the order of ∼2–5 μm.     

Influence of morphology and surface characteristics on the photocatalytic activity of rutile titania nanocrystals

This article presents the synthesis of phase-pure rutile titania with different morphologies via hydrothermal method at significantly low temperatures (40-150 °C) without any additives and their application as efficient photocatalyst for environmental remediation. Phase and morphology has been determined with X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ultra violet diffuse reflectance spectroscopy (UV-DRS) shows the optical band-gap in the range of ∼2.8-3.1 eV and Brunauer-Emmett-Teller specific surface area is found to be between 70 and 140 m²/g depending on the synthesis conditions. Raman spectroscopic analyses of the samples provide valuable insights into the structural and stoichiometric details. Photodegradation of the pollutant azo-dye, methyl orange (MO) in presence and absence of oxygen was performed to study the photocatalytic efficiency of the synthesized materials. Complete photodegradation of the dye is confirmed with high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) study. Dependence of dye photodegradation rate on morphology, specific surface area, surface nonstoichiometry and acidity were investigated in detail. Catalyst performance was compared from the rate constants obtained for each reaction using non-linear least square fitting (NLSF) to the experimental data in a concentration ratio (C₀/C_t) versus time (t) plot which shows extraordinarily high activity for all samples compared to commercial reference. Among them the catalyst synthesized at 40 °C for 16 h showed best activity. Kinetic study of the reaction matches well with simulated fit to experimental data and confirms to be pseudo-first order reaction.     

Preparation of AlVO4-films for sensor application via a sol-gel/spin-coating technique

The preparation of thin AlVO₄ films on corundum substrates for possible sensor application is described. Thermally stable, crack-free thin films having thicknesses typically below 0.1 μm were obtained by a sol-gel process using alkoxide reagents combined with a spin-coating technique. The films were structurally characterized by XRD, Raman and FTIR spectroscopy and their morphology was analyzed by SEM. XRD showed that the films consisted almost exclusively (> 90%) of AlVO₄ after calcination at 923 K.