Hybrid catalyst containing nano-sized LaMnO3 and carbon black for high yield and selective ketonization of n-butanol

An attempt has been made to synthesize a two-component hybrid material for highly selective catalytic ketonization of n-butanol. The perovskite-type oxide nano-crystallites were synthesized in the presence of carbon black particles by thermal transformation of equimolar mixture of lanthanum and manganese hydroxides into the perovskite-type oxide. The two-component material was tested as a catalyst for unconventional conversion of n-butanol to heptanone-4. The catalyst exhibited very high selectivity and yield towards the products, despite low content of LaMnO₃ in the two-component material (less than 10% by weight). The low oxide content led to the reduction of the cost of catalyst fabrication and is compensated by its high dispersion (grains ca. 20-30 nm in diameter) providing high conversion and yield comparable to pure-oxide catalysts. Catalyst fabrication is simple and environment friendly since it does not require organic solvents and excess amount of heavy metals (La and Mn).     

Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

The CaFe₂O₄ spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 °C which was lower than that of ferrite prepared by other methods. CaFe₂O₄ catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H₂O₂ (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H₂O₂ molar ratio and solvents on the conversion and product distribution were studied.     

The catalytic behavior of zinc oxide prepared from various precursors and by different methods

Samples of zinc oxide were obtained by thermal decomposition of zinc salts (acetate and nitrate) and by precipitation (chloride and nitrate). The samples were characterized by S_BET, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and scanning electron microscopy (SEM). XRD showed that ZnO crystals exhibited similar morphologies, while the crystal size and the particles morphology, availed by SEM, are dependent on the preparation method and the precursor salt utilized. The catalytic properties were evaluated to sec-butyl alcohol (SBA) reaction, using nitrogen, hydrogen and synthetic air as carrier gas. The catalytic properties of ZnO surface are strongly dependent on crystal size, atmosphere of reaction and zinc salts precursor. The activity to dehydrogenation of SBA in oxidant atmosphere is strongly sensitive to crystal size, while the selectivity to methyl ethyl ketone (MEK) is slightly sensitive. The activity to dehydrogenation and dehydration of SBA increases with change of atmosphere reaction from oxidant to reducing. High reaction temperatures and reducing environment for ZnO sample with small crystal size decrease significantly the selectivity to MEK. The ZnO crystal size has an important role to establish the properties of partial reduction of ZnO and catalytic properties.     

Low temperature synthesis of porous copper/zinc oxide

A two-step urea aqueous solution process at a low temperature (90 °C) was employed for the preparation of a copper/zinc oxide material. Well defined porous spherical particles with average sizes of around 5 μm in diameter were prepared first and then used as a support for further copper-zinc precipitation. It was found that the particle composition and shape were changed with applied stirring speed (100 rpm or 200 rpm) and that particle size is inversely proportional to the copper content in the particles. The particles preserved their size and shape after the heat treatment. Prepared Cu/ZnO samples showed catalytic activity for the reaction of steam reforming of methane. Samples were characterized by scanning field emission electron microscopy, energy dispersive X-ray analyses, X-ray powder diffraction, surface area analyses, and atomic absorption spectroscopy.     

Novel solar light driven photocatalyst, zinc indium vanadate for photodegradation of aqueous phenol

In the present investigation, we have demonstrated the synthesis of novel photocatalyst, zinc indium vanadate (ZIV) by solid-solid state route using respective oxides of zinc, indium and vanadium. This novel photocatalyst was characterized using XRD, FESEM, UV-DRS and FTIR in order to investigate its structural, morphological and optical properties. XRD clearly shows the formation of phase pure ZIV of triclinic crystal structure with good crystallinity. FESEM micrographs showed the clustered morphology having particle size between 0.5 and 1 μm. Since, optical study showed the band gap around 2.8 eV, i.e. in visible region, we have performed the photocatalytic activity of phenol degradation under visible light irradiation. The photodecomposition of phenol by ZIV is studied for the first time and an excellent photocatalytic activity was obtained using this novel photocatalyst. Considering the band gap of zinc indium vanadate in visible region, it will also be the potential candidate for water splitting.     

Synthesis of perovskite-type (La1−xCax)FeO3 (0 ≤ x ≤ 0.2) at low temperature

Gel formation was realized by adding citric acid to a solution of La(NO₃)₃·5H₂O, Ca(NO₃)₂·4H₂O, and Fe(NO₃)₂·9H₂O. Perovskite-type (La_1−xCa_x)FeO₃ (0 ≤ x ≤ 0.2) was synthesized by firing the gel at 500 °C in air for 1 h. The crystallite size (D_1 2 1) decreased with increasing x, while the specific surface area was 6.8-9.4 m²/g and independent of x. The XPS measurement of the (La_1−xCa_x)FeO₃ surface indicated that the Ca²⁺ ion content increased with increasing x, while the Fe ion content was independent of x. Catalytic activity for CO oxidation increased with increasing x.     

Photocatalytic properties of BiVO4 prepared by the co-precipitation method: Degradation of rhodamine B and possible reaction mechanisms under visible irradiation

Bismuth vanadate (BiVO₄) was synthesized by the co-precipitation method at 200 °C. The photocatalytic activity of the oxide was tested for the photodegradation of rhodamine B under visible light irradiation. The analysis of the total organic carbon showed that the mineralization of rhodamine B over a BiVO₄ photocatalyst (∼40% after 100 h of irradiation) is feasible. In the same way, a gas chromatography analysis coupled with mass spectroscopy revealed the existence of organic intermediates during the photodegradation process such as ethylbenzene, o-xylene, m-xylene, and phthalic anhydride. The modification of variables such as dispersion pH, amount of dissolved O₂, and irradiation source was studied in order to know the details about the photodegradation mechanism.     

Visible-light-driven NaTaO3−xNx catalyst prepared by a hydrothermal process

NaTaO_3−xN_x catalyst has been successfully synthesized from N-doped Ta₂O₅ precursors by a simple hydrothermal process. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. Density functional theory calculations suggested that the valence band of the catalysts was composed of the hybrid O 2p and N 2p orbitals, and the visible-light sensitivity is due to the narrowing of the band gap by mixing N 2p and O 2p states. NaTaO_3−xN_x catalyst could decompose the gaseous formaldehyde under the visible-light irradiation (λ > 400 nm), and its photocatalytic activity depended on N dopant concentration. NaTaO_2.943N_0.047 showed the highest photoactivity for the formaldehyde photodegradation.     

Ligand-assisted hydrothermal synthesis of ZnWO4 rods and their photocatalytic activities

ZnWO₄ rods were prepared using a ligand-assisted hydrothermal method with ZnCl₂ and Na₂WO₄ in the presence of various amines as ligands for zinc ions. The choice of ligand was found to play an important role in the formation of ZnWO₄ rods. The aspect ratio of the ZnWO₄ rods increased with increasing ligand strength. XRD and HRTEM confirmed that the ZnWO₄ rods grow along the [1 0 0] direction. The photochemical activities of the ZnWO₄ rods for the decomposition of Rhodamine 6G were examined. The photocatalytic activity was found to depend on the aspect ratio of the ZnWO₄ rods.     

TiO2 supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

TiO₂ nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N₂-sorption and UV-Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO₂/SBA-15 composite was prepared by loading TiO₂ nanoparticles on uniform rod-like SBA-15 of 1 μm length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.     

Synthesis of non-stoichiometric Bi2O4−x by oxidative precipitation

Bi₂O_4−x, a Bi mixed-valence phase was prepared at 95 °C, by a precipitation process, in a basic medium with a highly oxidizing K₂S₂O₈/Na₂S₂O₈. This phase has a low thermal stability as it decomposes below 400 °C in a multiple step process by some O₂ losses prior to finally transforming into γ-Bi₂O₃. The as-prepared powders are 50-60 nm in size with a narrow size distribution. Optical spectra of Bi₂O_4−x exhibit a broad absorption band with a band gap of ∼1.4 eV as compared to 2.61 eV for Bi₂O₃. The composition of this non-stoichiometric phase, which crystallizes in cubic fluorite related structure with a cell parameter of 5.538(3) Å, is Bi₂O_{3.65 ± 0.10}.     

Carbon nanotube-induced preparation of vanadium oxide nanorods: Application as a catalyst for the partial oxidation of n-butane

A vanadium oxide-carbon nanotube composite was prepared by solution-based hydrolysis of NH₄VO₃ in the presence of carbon nanotubes. The carbon nanotubes induce the nucleation of the 1D vanadium oxide nanostructures, with the nuclei growing into long freestanding nanorods. The vanadium oxide nanorods with the lengths up to 20 μm and the widths of 5-15 nm exhibit a well-ordered crystalline structure. Catalytic tests show that the composite with nanostructured vanadium oxide is active for the partial oxidation of n-butane to maleic anhydride at 300 °C.     

Phase selection and visible light photo-catalytic activity of Fe-doped TiO2 prepared by the hydrothermal method

It is necessary to extend the absorption range of TiO₂ based materials from the ultraviolet to the visible light region for most photo-catalytic applications of TiO₂ under solar irradiance or indoor lighting. Also, the ability to control the structural evolution, particularly the competition and transformation between different phases (anatase or rutile), is extremely important for the preparation of high efficiency TiO₂ based photo-catalysts. In this work, we have systematically studied the effects of various processing factors on the phase selection process/outcome of nanocrystalline Fe-doped TiO₂, which includes the level of doping ions, annealing temperature, solution pH and the addition of acidic anions, using a low temperature hydrothermal method. Both Fe-doped rutile and anatase TiO₂ phases were obtained via varying the processing conditions. The visible-light photo-catalytic activity of doped materials was significantly improved over that of the pure TiO₂ nanopowders, which was demonstrated by effective degradation of methylene blue under visible light.     

Synthesis, structure and oxygen-storage capacity of Pr1−xZrxO2−δ and Pr1−x−yPdyZrxO2−δ

Nanocrystalline Pr_1−xZr_xO_2−δ (0 ≤ x ≤ 1) and Pr_1−x−yPd_yZr_xO_2−δ (x = 0.50, y = 0.02) solid solutions have been synthesized by a single step solution combustion method. The whole range of solid solution compositions crystallize in cubic fluorite structure. The lattice parameter ‘a’ linearly varied up to x = 1.0. Oxygen-storage capacity (OSC) and redox properties of Pr_1−xZr_xO_2−δ (0.0 ≤ x ≤ 0.8) solid solutions have been investigated by temperature-programmed reduction (TPR) and are compared with those of Ce_1−xZr_xO₂. Pr_1−xZr_xO_2−δ exhibited H₂ uptake and CO oxidation at a lower temperature than Ce_1−xZr_xO₂. Small amount of Pd ion (y = 0.02) substitution was found to bring down the temperature of oxygen release-storage significantly.     

Solution combustion synthesis of γ(L)-Bi2MoO6 and photocatalytic activity under solar radiation

The facile method of solution combustion was used to synthesize γ(L)-Bi₂MoO₆. The material was crystallized in a purely crystalline orthorhombic phase with sizes varying from 300 to 500 nm. Because the band gap was 2.51 eV, the degradation of wide variety of cationic and anionic dyes was investigated under solar radiation. Despite the low surface area (<1 m²/g) of the synthesized material, γ(L)-Bi₂MoO₆ showed high photocatalytic activity under solar radiation due to its electronic and morphological properties.     

Structural properties and growth mechanism of flower-like ZnO structures obtained by simple solution method

Flower-shaped zinc oxide (ZnO) structures have been synthesized in the reaction of aqueous solution of zinc nitrate and NaOH at 90 °C. To examine the morphology of ZnO nanostructures, time-dependent experiments were carried out. Detailed structural observation showed that the flower-like structures consist of triangular-shaped leaves, having sharpened tips with wider bases. Photoluminescence spectrum measured at room temperature show a sharp UV emission at 381 nm and a strong and broad green emission at 480-750 nm attributed to structural defects. A possible growth mechanism for the formation of flower-shaped ZnO structures is discussed in detail.     

The cation inversion and magnetization in nanopowder zinc ferrite obtained by soft mechanochemical processing

Two zinc ferrite nanoparticle materials were prepared by the same method – soft mechanochemical synthesis, but starting from different powder mixtures: (1) Zn(OH)₂/α-Fe₂O₃ and (2) Zn(OH)₂/Fe(OH)₃. In both cases a single phase system was obtained after 18 h of milling. The progress of the synthesis was controlled by X-ray diffractometry (XRD), Raman spectroscopy, TEM and magnetic measurements. Analysis of the XRD patterns by Rietveld refinement allowed determination of the cation inversion degree for both obtained single phase ZnFe₂O₄ samples. The sample obtained from mixture (1) has the cation inversion degree 0.3482 and the sample obtained from mixture (2) 0.400. Magnetization measurements were confirmed that the degrees of the inversion were well estimated. Comparison with published data shows that used method of synthesis gives nano powder samples with extremely high values of saturation magnetizations: sample (1) 78.3 emu g⁻¹ and sample (2) 91.5 emu g⁻¹ at T = 4.5 K.     

Nitrogen-doped TiO2 nanotubes with enhanced photocatalytic activity synthesized by a facile wet chemistry method

Nitrogen-doped TiO₂ nanotubes with enhanced photocatalytic activity were synthesized using titanate nanotubes as raw material by a facile wet chemistry method. The resulting nanotubes were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, and UV-vis absorption spectroscopy, etc. The photocatalytic activity of nitrogen-doped TiO₂ nanotubes was evaluated by the decomposition of methylene blue under artificial solar light. And it was found that nitrogen-doped TiO₂ nanotubes exhibited much higher photocatalytic activity than undoped titanate nanotubes.     

Proton transport and structural relations in hydroxyl-bearing BaTiO3 and its doped compositions synthesised by wet-chemical methods

Hydrothermally synthesised powders of BaTiO₃ and its Fe- or Nd-doped analogues contain hydroxyl groups in the lattice substitutional to oxide ion, as confirmed from TGA/DTA, IR spectral analysis of D₂O-treated powders, EGA-MS, the contraction in lattice constant with heat treatment by XRD and surface examination by XPS. Electrical resistivity measurements were carried out on the pellets from 298 to 1000 K by ac impedance spectroscopy and dc methods in dry or moist air and 8% H₂+Ar environments. The electrical conductivity observed for unsintered pellets between 298 and 500 K, is in the range of 10⁻³ to 10⁻⁷ S/cm and can be attributed to the extrinsic hydroxyls in BaTiO₃. The acceptor-doped composition, BaTi_0.9Fe_0.1O_3−δ: 2δ(OH) exhibits higher electrical conductivity than BaTiO₃ or the donor-doped Ba_0.9Nd_0.1TiO_3−δ: 2δ(OH) in moist air. The hydrothermally prepared powders heat treated below 1000 K having cubic symmetry at room temperature, possess higher proton conductivity and reabsorption capability for hydroxyls on exposure to moisture than the powders sintered at 1673 K (tetragonal symmetry). The conductivity at 298-500 K is due to the mobility of proton along OHO octahedra in the perovskite lattice. The conduction at 550-1000 K is a combined effect of proton as well as oxygen vacancy mobility in BaTiO₃ and Ba_0.9Nd_0.1TiO₃; electron hole (Ti⁴⁺, Ti³⁺, Fe³⁺, Fe²⁺) participation is the additional contribution in acceptor-doped composition in this temperature range.     

Ba3ZnTa2−xNbxO9 and Ba3MgTa2−xNbxO9 (0≤x≤1): synthesis, structure and dielectric properties

Oxides belonging to the families Ba₃ZnTa_2−xNb_xO₉ and Ba₃MgTa_2−xNb_xO₉ were synthesized by the solid state reaction route. Sintering temperatures of 1300°C led to oxides with disordered (cubic) perovskite structure. However, on sintering at 1425°C hexagonally ordered structures were obtained for Ba₃MgTa_2−xNb_xO₉ over the entire range (0≤x≤1) of composition, while for Ba₃ZnTa_2−xNb_xO₉ the ordered structure exists in a limited range (0≤x≤0.5). The dielectric constant is close to 30 for the Ba₃ZnTa_2−xNb_xO₉ family of oxides while the Mg analogues have lower dielectric constant of ∼18 in the range 50 Hz to 500 kHz. At microwave frequencies (5-7 GHz) dielectric constant increases with increase in niobium concentration (22-26) for Ba₃ZnTa_2−xNb_xO₉; for Ba₃MgTa_2−xNb_xO₉ it varies between 12 and 14. The “Zn” compounds have much higher quality factors and lower temperature coefficient of resonant frequency compared to the “Mg” analogues.