Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Synthesis of Hollow Nanotubes of Zn2SiO4 or SiO2: Mechanistic Understanding and Uranium Adsorption Behavior

We report a facile synthesis of Zn2SiO4 nanotubes using a two-step process consisting of a wet-chemical synthesis of core-shell ZnO@SiO2 nanorods followed by thermal annealing. While annealing in air leads to the formation of hollow Zn2SiO4, annealing under reducing atmosphere leads to the formation of SiO2 nanotubes. We rationalize the formation of the silicate phase at temperatures much lower than the temperatures reported in the literature based on the porous nature of the silica shell on the ZnO nanorods. We present results from in situ transmission electron microscopy experiments to clearly show void nucleation at the interface between ZnO and the silica shell and the growth of the silicate phase by the Kirkendall effect. The porous nature of the silica shell is also responsible for the etching of the ZnO leading to the formation of silica nanotubes under reducing conditions. Both the hollow silica and silicate nanotubes exhibit good uranium sorption at different ranges of pH making them possible candidates for nuclear waste management.

Stabilization of a Tetrahedral (Mn5+O4) Chromophore in Ternary Barium Oxides as a Strategy toward Development of New Turquoise/Green-Colored Pigments

An experimental investigation of the stabilization of the turquoise-colored chrornophore (Mn5+O4) in various oxide hosts, viz., A(3)(VO4)(2) (A = Ba, Sr, Ca), YVO4, and Ba2MO4 (M = Ti, Si), has been carried out. The results reveal that substitution of Mn5+O4 occurs in Ba-3(VO4)(2) forming the entire solid solution series Ba-3(V1-x MnxO4)(2) (0 < x <= 1.0), while with the corresponding strontium derivative, only up to about 10% of Mn5+O4 substitution is possible. Ca-3(VO4)(2) and YVO4 do not stabilize Mn5+O4 at all. With Ba2MO4 (M = Ti, Si), we could prepare only partially substituted materials, Ba2M1-xMn5+O4+x/2 for x up to 0.15, that are turquoise-colored. We rationalize the results that a large stabilization of the O 2p-valence band states occurs in the presence of the electropositive barium that renders the Mn5+ oxidation state accessible in oxoanion compounds containing PO43-, VO43-, etc. By way of proof-of-concept, we synthesized new turquoise-colored Mn5+O4 materials, Ba-5(BO3)(MnO4)(2)Cl and Ba-5(BO3)(PO4)(MnO4)Cl, based on the apatite-Ba-5(PO4)(3)Cl-structure.

Electronic structure and surface properties of SrBi2Ta2O9 and related oxides

The electronic structure of SrBi2Ta2O9 and related oxides such as SrBi2Nb2O9, Bi2WO6 and Bi3Ti4O12 have been calculated by the tight-binding method. In each case, the band gap is about 4.1 eV and the band edge states occur on the Bi-O layers and consist of mixed O p/Bi s states at the top of the valence band and Bi p states at the bottom of the conduction band. The main difference between the compounds is that Nb 5d and Ti 4d states in the Nb and Ti compounds lie lower than the Ta 6d states in the conduction band. The surface pinning levels are found to pin Schottky barriers 0.8 eV below the conduction band edge.

Crystal structure and phase transition studies in perovskite-type oxides using powder-diffraction techniques and symmetry-mode analysis : SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) and ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm)

La tesis se ha centrado en la síntesis y caracterización estructural de materiales tipo perovskita: SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni,Fe) y ALn2CuTi2O9 (A=Ca,Ba; Ln=La,Pr,Nd,Sm). El estudio de las estructuras de los materiales se ha realizado mediante el análisis de los patrones de difracción en polvo de rayos-X, sincrotrón y/o neutrones. En el refinamiento por el método de Rietveld de las estructuras se han sustituido las coordenadas atómicas (el método más común), por coordenadas colectivas: las amplitudes de los modos que describen la distorsión de la fase prototipo. Los resultados generales para la serie SrLnMRuO6 (Ln=La,Pr,Nd; M=Zn,Co,Mg,Ni) a temperatura ambiente se ha recogido en un diagrama en el que se han indicado las amplitudes de los modos que transforman de acuerdo a las irreps en función del factor de tolerancia, ya que todos ellos cristalizan en la misma fase monoclínica (P21/n); y a temperaturas altas se ha construido un diagrama de fase. Los materiales SrLnFeRuO6 ( Ln=La,Pr,Nd) y CaLn2CuTi2O9 cristalizan en la fase ortorrómbica Pbnm a temperatura ambiente; mientras que BaLn2CuTi2O9 tienen una estructura más simétrica, I4/mcm. A altas temperaturas se han identificado las transiciones de fase inducidas por el cambio de temperatura.A temperaturas bajas se han analizado las estructuras magnéticas de algunos de los compuestos mediante difracción de neutrones.

Stereoselective inverse conjugate addition of nitrogen and carbon nucleophiles to allenyl phosphine oxide. Synthesis of α,β-unsaturated phosphine oxides

Issue in Honor of Prof. Paweł Kafarski