Conductivity of SnO<Subscript>2</Subscript>-In<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystalline composite films

The conductivity of films consisting of a mixture of SnO₂ and In₂O₃ nanocrystals at 200–500°C was studied. Based on the experimental data, it was assumed that in films containing less than 20 wt % In₂O₃, the current flows along SnO₂ nanocrystals. A model of conductivity in these films is presented; it includes an electron transfer from In₂O₃ to SnO₂, which forms positively charged In₂O₃ nanocrystals that contact the negatively charged SnO₂ nanocrystals. In the presence of In₂O₃ nanocrystals, the activation energy of the electron transfer between SnO₂ nanocrystals decreased substantially because of a decrease in the barrier of electron transfer between SnO₂ crystals under the action of the negative charge. As a result, a percolation cluster of charged SnO₂ crystals formed. At high contents of In₂O₃ (over 20 wt %), the conductivity increased dramatically. The curve of the temperature dependence of conductivity changed because of the appearance of a percolation cluster of In₂O₃ nanocrystals, in which the current passed. The conductivity of a mixed film of this kind differed from that of the nanocrystalline film of pure In₂O₃.     

Controlled synthesis,characterization and thermal properties of Mg<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>

Optimum conditions for synthesizing monoclinic and triclinic Mg₂B₂O₅ compounds by high-temperature solid-state reactions were investigated. Mixtures composed of boric acid and magnesium oxide at MgO:B₂O₃ mole ratios of 1:0.25, 1:0.5 and 1:1.5 were heated for 1 hour at temperatures between 600–1050°C and the formed phases were identified by XRD analysis. Monoclinic Mg₂B₂O₅ was formed by heating at 850°C for 4 hours together with minimum amounts of triclinic Mg₂B₂O₅, while triclinic Mg₂B₂O₅ was formed as a single phase at 1050°C for the same reaction time. The products obtained at optimum conditions were subjected to a series of tests to determine their chemical compositions, particle size distributions, surface area values, IR spectra and TG/DTA patterns.      

Sensors based on SnO<Subscript>2</Subscript> + In<Subscript>2</Subscript>O<Subscript>3</Subscript> composite films for detecting CO in air

The sensor properties of nanostructured films of SnO₂, In₂O₃, and their combinations for detecting CO in air in the temperature range of 330–520°C were investigated. It was found that SnO₂ films show the least sensitivity to CO. Sensitivity grows as the concentration of In₂O₃ in SnO₂ increases, and it reaches its maximum value in pure In₂O₃. At the same time, the maximum of sensitivity to CO in air shifts towards low temperatures. Sensor response time was found to be about 1 s for the studied SnO₂ and In₂O₃ films, and about 0.5 s for the composite film. The mechanism of sensor sensitivity for the studied metal oxide films in detecting CO in air is discussed.     

Phase relations in the CaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system in the subsolidus region

Phase relations in the CaO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction and differential thermal analyses, and the isothermal section at 600°C has been constructed. The formation of ternary compounds at the component ratios 1CaO: 1Bi₂O₃: 1B₂O₃ (CaBi₂B₂O₇) and 1CaO: 1Bi₂O₃: 2B₂O₃ (CaBi₂B₄O₁₀) has been established X-ray diffraction characteristics of these phases are presented.     

Catalytic properties of SnO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> compositions in total methane oxidation

Tin and titanium dioxides and their compositions were studied as catalysts for the reaction of complete oxidation of methane. The catalytic activity of the test samples was compared in terms of first-order reaction rate constants with reference to the unit surface area of a catalyst. The crystal structures and specific surface areas of the obtained compositions were characterized. The thermal stability of SnO₂ was investigated. Data on the temperature-programmed reduction of SnO₂ and the composition Sn_0.70Ti_0.30O₂ in hydrogen were given.     

Eu<Superscript>3+</Superscript>-fluorescence properties in nano-crystallized SnO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

Fluorescence and spectral hole burning properties of Eu³⁺ ions were studied in nanocrystals-precipitated SnO₂-SiO₂ glasses. The glasses were prepared to contain various amount of Eu₂O₃ using the sol-gel method, in which SnO₂ nanocrystals were precipitated by heating in air. In the glasses containing Eu₂O₃ less than 1%, the Eu³⁺ ions were preferentially doped in the SnO₂ nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO₂ crystals. The SnO₂ nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu³⁺ ions. With the increasing Eu₂O₃ concentration, the amount of SnO₂ nanocrystals decreased and the Sn⁴⁺ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.     

Thermal analysis of binary system Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SnO<Subscript>2</Subscript> obtained by sol-gel technique

Summary A series of Al₂O₃-SnO₂ catalysts with Al₂O₃ to SnO₂ molar ratio of 1:1, 1:0.5, 1:0.2 and 1:0.1 were synthesized by sol-gel technique and characterized by thermal analysis and FTIR. In the case of binary gels - addition of tin component leads to better crosslinking than in pure alumina gel and as a result to a much uniform texture structure.     

The influence of structural factors on the gas-sensitive properties of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-SnO<Subscript>2</Subscript>

The influence of the dispersity and structural and phase state of oxide materials based on Fe₂O₃ and SnO₂ on the gas-sensitive properties of these materials used as sensitive layers in chemical sensors was considered. It was found that high-dispersity Fe₂O₃-SnO₂ (Fe: Sn = 9: 1) ceramic layers possessed high sensitivity to ethanol vapor in both dry and humid atmosphere and low sensitivity to CO and CH₄. The maximum response to ethanol vapor in humid atmosphere was characteristic of layers with structures of substitution-interstitial solid solutions of Sn⁴⁺ in α-Fe₂O₃.     

Chemical composition optimization and characterization of the NiO/B<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system as a catalyst for ethylene oligomerization

The samples of the NiO/B₂O₃-Al₂O₃ system with NiO contents from 0.48 to 38.30 wt % were synthesized by the impregnation of borate-containing alumina (20 wt % B₂O₃). It was found that nickel oxide occurred in an X-ray amorphous state in the samples containing to 23.20 wt % NiO. At a NiO content of 4.86 wt % or higher, the support was blocked by the modifier to cause a decrease in the specific surface area from 234 to 176 m²/g and in the amount of acid sites from 409–424 to 333 μmol/g. An extremal character of the dependence of catalyst activity in ethylene oligomerization on NiO content was found with a maximum in the range of 4.86–9.31 wt %. Based on spectroscopic data, it was found that ethylene activation on the NiO/B₂O₃-Al₂O₃ catalyst can be associated with the presence of Ni²⁺ cations, which chemically interact with the support. The catalyst containing 4.86 wt % NiO at 200°C, a pressure of 4 MPa, and an ethylene supply rate of 1.1 h⁻¹ provided almost complete ethylene conversion at the yield of liquid oligomerization products to 90.0 wt %; the total concentration of C⁸⁺ alkenes in these products was 89.0 wt %.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> phase diagram

Phase relations in the Y₂O₃-Ga₂O₃ system were studied by the anneal-and-quench technique in air within 1000–2300°C, and a phase diagram was plotted. Three compounds were found to form: Y₃GaO₆, Y₄Ga₂O₉, and Y₃Ga₅O₁₂; the temperature and concentration bounds of stability were determined for these compounds. Indexing results for Y₃GaO₆ are given.     

High-temperature X-ray study of the formation and delamination of manganese-alumina spinel Mn<Subscript>1.5</Subscript>Al<Subscript>1.5</Subscript>O<Subscript>4</Subscript>

The behavior of the manganese-alumina system with Mn:Al = 1:1 on heating in air and vacuum was studied. The starting samples were mixtures of β-Mn₃O₄, α-Mn₂O₃, and γ-Al₂O₃. On heating to 950°C in air, the samples were partially oxidized into α-Mn₂O₃, and corundum α-Al₂O₃ formed along with mixed manganese-alumina cubic spinel, whose composition was close to Mn₂AlO₄. In vacuum at 1200°C, the starting sample with a ratio of Mn:Al = 1:1 transformed into the manganese-alumina spinel Mn_1.5Al_1.5O₄, which retained its cubic structure after slow cooling in vacuum. When cooled in air, this solid solution delaminated, and a nanocrystalline Mn_2.8Al_0.2O₄ phase formed, whose structure was β-Mn₃O₄ type tetragonal spinel.     

Synthesis and crystal structure of strontium borate Sr<Subscript>4</Subscript>B<Subscript>14</Subscript>O<Subscript>25</Subscript>

The new compound Sr₄B₁₄O₂₅ (4SrO · 7B₂O₃) corresponding to an oxide ratio of 4: 7 has been identified and synthesized in the SrO-B₂O₃ system. The crystal structure of the compound has been determined (space group Cmc2₁, a = 7.734(5) Å, b = 16.332(5) Å, c = 14.556(5) Å, Z = 4, 702 F(hkl), R = 0.078). The borate anions form a three-dimensional framework consisting of borate groups of two types: three-ring structures (2□, Δ) and BO₃ triangles. Layers formed by 14-membered rings composed of boron-oxygen tetrahedra and triangles packed within the layer according to the herringbone pattern can be distinguished in the framework. The strontium atoms are located on the mirror symmetry planes between these layers. The compound is metastable and decomposes, on long-term storage, into strontium di- and metaborate.     

No-Glycerol rapid heterogeneous biodiesel production on K<Subscript>2</Subscript>CO<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst by coupling process

Biodiesel containing almost no glycerol has been produced by coupling reaction carried out over K₂CO₃ supported by calcium oxide as solid base catalysts. The solid base catalysts synthesized by wet impregnation exhibit an exceedingly high activity in biodiesel production. It was found that the reaction time required for the highest yield of biodiesel, 99.2%, can be shortened to 30 min over K₂CO₃/Al₂O₃ under the optimum reaction conditions: 8: 1: 1 molar ratio of methanol/DMC/oil, 30 wt % K₂CO₃/Al₂O₃ catalyst, and 65°C reaction temperature. Solid basic catalysts examined in the study were characterized by BET surface area, XRD, CO₂-TPD, and SEM techniques. The strong interaction between K₂CO₃ and the support yields a new basic active site, which can be probably responsible for the high activity of K₂CO₃/Al₂O₃.     

Thermodynamic properties of silicate glasses and melts: V. Systems CaB<Subscript>2</Subscript>O<Subscript>4</Subscript>-CaSiO<Subscript>3</Subscript> and Ca<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>5</Subscript>-CaSiO<Subscript>3</Subscript>

Thermodynamic properties of melts of the CaB₂O₄-CaSiO₃ and Ca₂B₂O₅-CaSiO₃ systems were determined by the method of high-temperature mass-spectrometry. The melts of these systems are characterized by negative deviations from the ideal behavior at 1800 K.     

Composition of the gas phase over Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and the enthalpies of atomization of AlO,Al<Subscript>2</Subscript>O,and Al<Subscript>2</Subscript>O<Subscript>2</Subscript>

The A1, O, AlO, A1₂O, Al₂O₂, WO₂, and WO₃, partial pressures in the vapor over Al₂O₃ in a tungsten Knudsen effusion cell between 2300 and 2600 K were derived from A1⁺, O⁺, AlO⁺, A1₂O⁺, Al₂O₂⁺, WO₂⁺, and WO₃⁺, ion intensities. The mass spectrometer was calibrated against the equilibrium constant of the WO₃(g) = WO₂(g) + O(g) reaction. Refined values of the ionization cross sections of AlO and A1₂O₂ were used in the partial pressure calculations. The enthalpies of atomization of aluminum suboxides were determined to be Δ_at H ^o(AlO, g, 0) = 510.7 ± 3.3 kJ mol⁻¹, Δ_at H ^o(Al₂O, g, 0) = 1067.2 ± 6.9 kJ mol⁻¹, and Δ_at H ^o(Al₂O₂, g, 0) = 1556.7 ± 9.9 kJ mol⁻¹.     

The phase diagram of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-MoO<Subscript>3</Subscript>-Ag<Subscript>2</Subscript>O system

The results concerning the synthesis, structure and thermal properties of V₂O₅-MoO₃-Ag₂O samples in the molybdenum rich region of ternary system are presented in the form of quasi-binary systems: β-AgVO₃-β-Ag₂MoO₄, AgVMoO₆-MoO₃, AgVMoO₆-Ag₂Mo₄O₁₃, AgVMoO₆-Ag₂Mo₂O₇, AgVMoO₆-β-Ag₂MoO₄ and also of the system in which at V₂O₅/MoO₃ molar ratio 3:7 the content of Ag₂O was variable. The ternary phase AgVMoO₆ was not described earlier in the literature.     

Voltammetric determination of vitamin B<Subscript>6</Subscript> (pyridoxine) at a graphite screen-printed electrode modified with graphene oxide/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> nanocomposite

The preparation and study of electrochemical properties of a graphite screen-printed electrode (SPE) modified with the GO/Fe₃O₄@SiO₂ (GO is graphene oxide) nanocomposites are described. The morphologies of the GO/Fe₃O₄@SiO₂ nanocomposites were examined by scanning electron microscopy. The electrochemical oxidation of vitamin B₆ (pyridoxine) on SPE modified with the GO/Fe₃O₄@SiO₂ nanocomposite was investigated by cyclic voltammetry, differential pulse voltammetry, and chronoamperometry. Under optimum conditions (pH 7.0), the vitamin B₆ oxidation at the surface of the modified SPE occurs at a potential about 190 mV less positive than that at the unmodified SPE. A linear voltammetric response for vitamin B₆ was obtained in the concentration range 1.0?10 ⁶—9.0?10 ⁴ mol L^–1 with a detection limit of 5.2?10 ⁷ mol L^–1 using differential pulse voltammetry. The developed sensor was also successfully applied for determination of trace level of vitamin B₆ in both the standard vitamin B₆ sample and biological samples (urine).     

Hydrothermal Syntheses and Crystal Structures of Two New Heteropolyoxovanadoborates Containing {(VO)<Subscript>12</Subscript>O<Subscript>6</Subscript>[B<Subscript>3</Subscript>O<Subscript>6</Subscript>(OH)]<Subscript>6</Subscript>(H<Subscript>2</Subscript>O)} Cluster

Two new heteropolyoxovanadoborates (H₂dap)₂H₆{(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)}·13H₂O (1, dap = 1,2-diaminopropane) and {[Zn(dien)]₂[Zn(dien)(H₂O)]₄(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)}₂·15H₂O (2, dien = diethylenetriamine) have been hydrothermally synthesized and structurally characterized. Both 1 and 2 contain {(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)} cluster (denoted on V₁₂B₁₈), which is constructed by a puckered B₁₈O₃₆(OH)₆ ring sandwiched between two triangles of six alternating cis and trans edge-sharing vanadium atoms, and a central water molecule. 1 consists of discrete [V₁₂B₁₈]¹⁰⁻ cluster anions with H₂dap²⁺ as counterions, while 2 consists of discrete neutral {[Zn(dien)]₂[Zn(dien)(H₂O)]₄[V₁₂B₁₈]} clusters, which are built from two types of zinc(II) complex fragments connecting with V₁₂B₁₈ cluster through two Zn-(μ ₃-O)-B bonds. Interestingly, 2 is the only example of the V₁₂B₁₈ cluster decorated by two types of zinc(II) complex fragments.     

Osmotic Coefficients of the Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>+LiCl + H<Subscript>2</Subscript>O System at <Emphasis Type="Italic">T</Emphasis>=273.15 K

Osmotic coefficients and water activities for the Li₂B₄O₇+LiCl+H₂O system have been measured at T=273.15 K by the isopiestic method, using an improved apparatus. Two types of osmotic coefficients, φ _S and φ _E, were determined. φ _S is based on the stoichiometric molalities of the solute Li₂B₄O₇(aq), and φ _E is based on equilibrium molalities from consideration of the equilibrium speciation into H₃BO₃,B(OH)₄⁻ and B₃O₃(OH)₄⁻. The stoichiometric equilibrium constants K _m for the aqueous speciation reactions were estimated. Two types of representations of the osmotic coefficients for the Li₂B₄O₇+LiCl+H₂O system are presented with ion-interaction models based on Pitzer’s equations with minor modifications: model (I) represents the φ _S data with six parameters based on considering the ion-interactions between three ionic species of Li⁺, Cl⁻, and B₄O₇²⁻, and model (II) for represents the φ _E data based on considering the equilibrium speciation. The parameters of models (I) and (II) are presented. The standard deviations for the two models are 0.0152 and 0.0298, respectively. Model (I) was more satisfactory than model (II) for representing the isopiestic data.     

Comparing the electrochemical properties of pure phase Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> and composite Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/C

Compound Zn₂SnO₄ was synthesized by a hydrothermal method in which SnCl₄ · 5H₂O, ZnCl₂ and N₂H₄ · H₂O were used as reactants. Composite Zn₂SnO₄/C was then synthesized through a carbothermic reduction process using the as-prepared Zn₂SnO₄ and glucose as reactants. Comparing to the pure Zn₂SnO₄, some improved electrochemical properties were obtained for composite Zn₂SnO₄/C. When doped with 15% glucose, the composite Zn₂SnO₄/C showed the best electrochemical performance. Its first discharge capacity was about 1500 mA h g⁻¹, with a capacity retain of 500 mA h g⁻¹ in the 40th cycle at a constant current density of 100 mA/g in the voltage range of 0.05–3.0 V. There were also some differences displayed in their cyclic voltammogram.