Catalytic behavior of AMoOx (A = Ba, Sr) in oxidation of 2-propanol

Perovskite-type oxides, BaMoO₃ and SrMoO₃, were prepared by reduction of scheelite-type oxides, BaMoO₄ and SrMoO₄, in H₂ flow at 873 K and characterized by XRD, TG, SEM, TPR, NH₃-TPD, UV-vis DRS and BET measurement. The catalytic activity of these alkaline-earth molybdenum oxide catalysts was tested for oxidation of 2-propanol with gaseous oxygen under atmospheric pressure. Dehydration to propylene was mainly promoted over the scheelite-type with Mo⁶⁺, while oxidative dehydrogenation to acetone was mainly promoted over the perovskite-type with Mo⁴⁺, and selectivity to acetone was much higher over BaMoO₃ than over SrMoO₃. Both perovskite-type oxide catalysts underwent oxidation to some degree during the catalytic reaction, so that they also contained some Mo⁶⁺. We concluded that the high selectivity to acetone resulting from oxidative dehydrogenation during 2-propanol conversion is related to the constantly changing oxidation state of the catalyst, resulting in coexistence of Mo⁶⁺ octahedra and Mo⁴⁺ octahedra on the AMoO₃ oxides.     

Quantification of the incorporation coefficient of a reactive gas on a metallic film during magnetron sputtering: The method and results

Reactive Magnetron Sputtering is a complex process and huge efforts are made addressing the understanding of its fundamental phenomena and the simulation of the deposition process by e.g. Particle in Cell/Monte Carlo (PIC/MC). One of the most uncertain parameters in this reactive sputtering process is the incorporation coefficient of the reactive gas in the growing layer, i.e. the real-time sticking coefficient during deposition. In this work, mass spectrometry is used to deliver more insights on this complex matter.Earlier, a method was developed to determine the incorporation coefficient of the reactive gas molecules in the growing metal film, using mass spectrometry combined with thin film analysis techniques (electron probe microanalysis and x-ray photoelectron spectroscopy). This method delivers a global, realistic incorporation coefficient which can be used in models for the reactive sputtering process. In this work, new insights have been added to the classical method. As previously only molecular reactive gas particles were considered, the here described method extends to determine the global incorporation coefficient of all reactive gas particles, i.e. both molecular as atomic. The incorporation coefficient of oxygen gas during the reactive magnetron sputtering of Cu, Al, Mg and Y, is determined. It can be concluded that for the first three metal systems, the obtained incorporation coefficient is mainly determined by the molecular oxygen, while for Y both atomic and molecular oxygen are important. Furthermore, a trend between the difference in electronegativity of the metal and the reactive gas, and the incorporation coefficient can be observed.     

Preparation of CaO as OLED getter material through control of crystal growth of CaCO3 by block copolymers in aqueous solution

As the starting materials of organic light-emitting diode (OLED) getter, calcium carbonate (CaCO₃) particles with various shapes and crystal structures have been successfully prepared with additives (L64 or PEGPG), which contain blocks of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO). These CaCO₃ particles were calcinated into highly crystalline calcium oxide (CaO) nanoparticles with high capacity of water adsorption up to 14.23 wt.%. The CaCO₃ and CaO particles prepared at various conditions were characterized using the field emission scanning electron microscopy (FE-SEM), Fourier transform infrared microscopy (FT-IR), X-ray powder diffraction (XRD), and dynamic vapor sorption (DVS) method.     

Investigation of RuO2-SnO2 thin film formation by thermogravimetry-mass spectrometry and infrared emission spectroscopy

The thermal evolution process of RuO₂-SnO₂/Ti mixed oxide thin films of varying noble metal content has been investigated by thermogravimetry-mass spectrometry and Fourier transform infrared emission spectroscopy. The gel-like films prepared from aqueous solutions of the precursor salts Sn(OH)₂(CH₃COO)_2−xCl_x and Ru(OH)Cl₃ on titanium metal support were heated in an atmosphere containing 20% O₂ and 80% Ar up to 873 K.Chlorine evolution takes place in a single stage process between 573 and 773 K, while the decomposition of organic species like various types of carbonyls, carbonates and carboxylates occurs in two main stages between 423 and 773 K. The combustion temperature of the organic species formed decreases with the increase of the ruthenium content, indicating the catalytic effect of the noble metal. The secondary processes can significantly influence the morphology and electrochemical properties of the films when used as anodes in electrochemical processes.     

Synthesis of well-crystallized birnessite using ethylene glycol as a reducing reagent

Well-crystallized birnessite sheets containing K⁺ in the interlayers have been prepared using KMnO₄, ethylene glycol and KOH by microwave heating at 90 °C for 10 min. Ethylene glycol was used as a reducing agent. The effect of KOH concentration on the formation of birnessite was studied. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TG), differential scanning calorimetric analysis (DSC) and Fourier transform infrared (FTIR). Birnessites were converted to cryptomelane upon heating at 400-800 °C and completely collapsed to form Mn₃O₄ at 1000 °C.     

6H hexagonal structure of low loss Ba3MTiWO9 (M = Mg, Zn) dielectrics

The crystal structure of Ba₃MTiWO₉ (M = Mg, Zn) oxides has been found to be 6H hexagonal, space group P6₃/mmc, parameters of unit cell: a = 5.7943(1) Å, c = 14.1642(1) Å and a = 5.7993(1) Å, c = 14.1626(1) Å for M = Mg and Zn, respectively. The tungsten and titanium atoms are randomly distributed in pairs of face-sharing octahedra separated by octahedral layers containing magnesium or zinc. It was revealed that the structures are well ordered which is believed to result in a low dielectric loss at a microwave frequency reported for these materials.     

Highly aluminium doped barium and strontium ferrite nanoparticles prepared by citrate auto-combustion synthesis

Aluminium doped barium and strontium hexaferrite nanoparticles BaAl_xFe_(12−x)O₁₉ and SrAl_xFe_(12−x)O₁₉ were synthesised via a sol-gel route using citric acid to complex the ions followed by an auto-combustion reaction. This method shows promise for the synthesis of complex ferrite powders with small particle size. It was found that around half of the iron could be substituted for aluminium in the barium ferrite with structure retention, whereas strontium aluminium ferrites could be produced with any aluminium content including total substitution of the iron. All synthesised materials consisted of particles smaller than 1 μm, which is the size of a single magnetic domain, and various doping levels were achieved with the final elemental composition being within the bounds of experimental error. The materials show structural and morphological changes as they move from iron to aluminium ferrites. Such materials may be promising for imaging applications.     

Optimized microwave dielectric properties of Co- and Ca-substituted Mg0.6Zn0.4TiO3

The system of (1 − y)(Mg_0.6Zn_0.4)_1−xCo_xTiO₃-yCaTiO₃ was investigated to optimize its microwave dielectric properties by adopting appropriate contents of Co and Ca and by controlling sintering conditions. The effect of Co substitution was to enhance densification and Qf value, while the addition of CaTiO₃ resulted in increases of dielectric constant and TCF. As an optimal compositions, 0.93(Mg_0.6Zn_0.4)_0.95Co_0.05TiO₃-0.07CaTiO₃ successfully demonstrated a dielectric constant of 23.04, a Qf of 79,460 GHz and a TCF value of +1.4 ppm/°C after firing at a relatively lower sintering temperature of 1200 °C. The increase of sintering temperature beyond 1200 °C tended to degrade overall microwave dielectric properties presumably due to Zn volatilization as evidenced by the presence of a Zn-deficient phase (MgTi₂O₅) at 1400 °C. An attempt to establish the correlation between microstructure characteristics and dielectric properties was made in this dielectric system where the extensive range of firing temperature up to 1400 °C was evaluated.     

Order-disorder phase transitions and high-temperature oxide ion conductivity of Er2+xTi2−xO7−δ (x = 0, 0.096)

The Er_2+xTi_2−xO_7−δ (x = 0.096; 35.5 mol% Er₂O₃) solid solution and the stoichiometric pyrochlore-structured compound Er₂Ti₂O₇ (x = 0; 33.3 mol% Er₂O₃) are characterized by X-ray diffraction (phase analysis and Rietveld method), thermal analysis and optical spectroscopy. Both oxides were synthesized by thermal sintering of co-precipitated powders. The synthesis study was performed in the temperature range 650-1690 °C. The amorphous phase exists below 700 °C. The crystallization of the ordered pyrochlore phase (P) in the range 800-1000 °C is accompanied by oxygen release. The ordered pyrochlore phase (P) exists in the range 1000−1200 °C. Heat-treatment at T ≥ 1600 °C leads to the formation of an oxide ion-conducting phase with a distorted pyrochlore structure (P2) and an ionic conductivity of about 10⁻³ S/cm at 740 °C. Complex impedance spectra are used to separately assess the bulk and grain-boundary conductivity of the samples. At 700 °C and oxygen pressures above 10⁻¹⁰ Pa, the Er_2+xTi_2−xO_7−δ (x = 0, 0.096) samples are purely ionic conductors.     

Synthesis and characterization of K2NiF4-type CaLnCoO4 (Ln = Sm and Gd)

K₂NiF₄-type CaLnCoO₄ (Ln = Sm and Gd) has been synthesized at 1173 or 1223 K in air using citric acid (CA) and ethylene glycol (EG). CaLnCoO₄ (Ln = Sm and Gd) has an orthorhombic structure with the space group Bmab. The average particle sizes are approximately 300 nm for CaSmCoO₄ and approximately 170 nm for CaGdCoO₄, respectively. The global instability index (GII) indicates that the crystal structure of CaGdCoO₄ is more stable than that of CaSmCoO₄. CaLnCoO₄ (Ln = Sm and Gd) is a p-type semiconductor and shows paramagnetic behavior above 5 K. The 1/χ-T curve of CaSmCoO₄ deviates from the Curie-Weiss law, whereas the 1/χ-T curve of CaGdCoO₄ follows the Curie-Weiss law in the temperature range of 5 ≤ T ≤ 300 K. From the values of the observed effective magnetic moment (μ_eff) of CaLnCoO₄ (Ln = Sm and Gd), it is considered that the spin state of the Co³⁺ ion is low.