The Symmetric and Topological Code of the Cluster Self-Assembly of the Crystal Structure of ε-Mg<Subscript>23</Subscript>Al<Subscript>30</Subscript> of K63 Nanoclusters

The geometrical and topological analysis of the crystal structure of intermetallide ε-Mg₂₃Al₃₀ (ToposPro program) with V = 3098.0 ų and space group R-3 is carried out. The symmetric and topological codes of the cluster self-assembly of the crystal structure are determined: primary chain S ₃ ¹ → microlayer S ₃ ² → microframework S ₃ ³ . A new type of nanocluster-precursor of the crystal structure, which is formed on the internal 13-atomic cluster, which represents a template and consists of two bound ridged rings Mg–Al–Mg–Al–Mg–Al with the central Mg atom, is discovered. A quasi-spherical deltahedron shell made from 50 atoms is formed on the template. The center of a K63 cluster occupies the position with the point symmetry 3? in the unit cell. There are six neighboring K63 clusters in the local environment of the K63 cluster in the layer. The basic 3D network, which characterizes the location of the gravity centers of the K63 clusters, corresponds to a hexagonal closely packed network (HCP, Mg type) with CN = 12. The localization of two Mg atoms in the pores of the framework is determined.     

Analysis of the Parameters of the Mössbauer Spectra and the Spectra of Nuclear Quadrupole Resonance of the Superconducting Ceramic YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript>

The parameters of the Mössbauer spectra on ⁶⁷Cu(⁶⁷Zn), ⁶⁷Ga(⁶⁷Zn) isotopes, and the data of nuclear quadrupole resonance on an ¹⁷O isotope are anlayzed, and the lattice gradient of the electric field for the crystal lattice YBa₂Cu₃O₇ is calculated. It is shown that these parameters correspond to the model when the hole is predominantly in the sublattice of the oxygen chain.     

Review of chemical syntheses of 7-keto-Δ<Superscript>5</Superscript>-sterols

Steroids bearing ketone functionality at carbon-7 are found commonly in nature, and the most prevalent of these are the 7-keto-Δ⁵-sterols. These substances have diverse biological properties and are present in biological samples and food products. For the purpose of studying this class of oxysterols, many chemical methods, involving the chemical oxidation of Δ⁵-sterols to the corresponding 7-keto-Δ⁵-sterols derivatives have been developed to produce these compounds. We have undertaken a review and evaluation of chemical methods for the synthesis of these compounds and have endeavored to enhance one of these procedures to yield products for chemical and biological investigations.     

Calculation of phase diagrams of heterophase two- and three-component liquid mixtures ‘α-pinene-water’ and ‘α-pinene-water-ethanol’

Phase behaviors of two- and three-component mixtures ‘α-pinene-water’ and ‘α-pinene-ethanol-water’ were studied over a wide range of their composition, temperature, and pressure. Conditions were found that provide heteroazeotropic states of binary mixture ‘α-pinene-water’ and ternary mixture ‘α-pinene-ethanol-water’ depending on the ratio of ‘water/(α-pinene+ethanol)’ fractions at the ‘α-pinene+ethanol’ ratio of 1:1. Critical curves were calculated to demonstrate an anomalous dependence of these curves on the mixture composition, with the temperature minimum points typical of the mixtures that form heteroazeotropes.     

Enhancement of the Activities of γ-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for Methane-SCR of NO by Treatment with NH<Subscript>3</Subscript>

Abstract  

The precursor particles for γ-Ga₂O₃–Al₂O₃ solid solutions were prepared by the coprecipitation method from aqueous solutions of Ga(NO₃)₃ and Al(NO₃)₃ with (NH₄)₂CO₃ as a precipitant. The γ-Ga₂O₃–Al₂O₃ solid solutions were obtained by calcination of the precursor at 700 °C. In this paper, the performance of the catalysts treated with NH₃ was investigated for the selective catalytic reduction (SCR) of NO with methane as a reducing agent, and it was found that γ-Ga₂O₃–Al₂O₃ catalysts treated with NH₃ and subsequently annealed in air showed higher activities than the γ-Ga₂O₃–Al₂O₃ catalysts without NH₃ treatment. NH₃ treatment of the catalyst caused partial rearrangement of Ga³⁺ and Al³⁺ ions and increased the population of tetrahedral Ga³⁺ ions in the defective spinel structure.     

Synthesis and research of nanopowders composed of 0.97ZrO<Subscript>2</Subscript> · 0.03La<Subscript>2</Subscript>O<Subscript>3</Subscript>

This work is devoted to the preparation of zirconium oxide nanopowders stabilized by lanthanum oxide using the method of codeposition in the presence of hydrogen peroxide. Nanopowders composed of 0.97ZrO₂ · 0.03La₂O₃ with particles of 10–20 nm are obtained. It is found that in the temperature interval of 500–1100°C the tetragonal and monoclinic points of the zirconium oxide phase crystallize at the same time.     

Crystallization Behavior of Lithium–Iron-Phosphate Glasses with Additions of ZrO<Subscript>2</Subscript>

Lithium–iron-phosphate (LIP) glasses with different amounts of zirconia were prepared by conventional melting and annealing process. The influence of the nucleation agent, zirconia, on the crystallization behavior of LIP glasses has been studied using differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electronic microscopy (SEM) techniques. The results show that addition of 2 wt% of zirconia results in increases in the glass transition and crystallization temperatures and a decrease in the activation energy of crystallization. However, both temperatures decrease with increased addition of zirconia while the activation energy increases. The zirconia-free LIP glass only shows surface crystallization with crystals of LiFeP₂O₇. The glass containing 2 wt% of zirconia also has surface crystallization; however, mixed ZrP₂O₇ and LiFeP₂O₇ are crystallized. The addition of 5 and 8 wt% of zirconia leads to bulk crystallization and increasing formation of ZrP₂O₇ crystals besides the LiFeP₂O₇ phase.     

Physicochemical Properties of Nanosized Powders of the LaPO<Subscript>4</Subscript>–DyPO<Subscript>4</Subscript>–H<Subscript>2</Subscript>O System

Nanosized La_1–xDy_xPO₄ · nH₂O powders are synthesized by the sol-gel method using direct and reverse precipitation. The formation of a continuous series of hexagonal solid solutions based on LaPO₄ · nH₂O is confirmed by the XRD and DSC/TG methods. A continuous series of monoclinic solid solutions based on LaPO4 is formed at temperatures higher than 600°C. A reflex corresponding to a tetragonal form of DyPO₄ is formed during the calcination of DyPO₄ powder at 850°C. Two types of solid solutions are observed at temperatures of 1000–1200°C, namely, monoclinic solutions based on LaPO₄ (to x ≈ 0.7) and tetragonal solutions based on DyPO₄ (0.90 ≤ x ≤ 1.0). The results are compared depending on the methods of nanopowder synthesis.     

Influence of the presence of bubbles on the parameters of crystal nucleation in the 26Li<Subscript>2</Subscript>O · 74SiO<Subscript>2</Subscript> glass

The crystal nucleation in the glass of composition (mol %) 26Li₂O · 74SiO₂ has been investigated in the cases of homogeneous and heterogeneous nucleation. Parameters of homogeneous nucleation, such as the stationary nucleation rate I _st, the time of nonstationary nucleation τ, and the crystal growth rate U, have been determined. The temperature dependences of these parameters have been constructed. The surface energy σ at the nucleus-glass melt interface has been determined, and its temperature dependence has been obtained. The surface energy σ has been evaluated using the graphical method for solving the transcendental equation derived by transforming the relationships for the stationary crystal nucleation rate and the time of nonstationary crystal nucleation. The critical nucleus sizes r* and the free energy of formation of the critical nucleus Φ* have been determined. The heterogeneous nucleation on bubbles specially produced in the glass has been studied. It has been demonstrated that the presence of bubbles in the initial glass does not affect the crystal growth rate and substantially changes the nonstationary nucleation rate. The largest contribution to the change in the nucleation rate is made by “active” bubbles (filled by water vapor) formed in the glasses synthesized with the use of hydrated silicon dioxide.     

Facile Synthesis of Ag–γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Superior Nanocomposite for Catalytic Reduction of Nitroaromatic Compounds and Catalytic Degradation of Methyl Orange

A facile synthetic route for preparing silver-doped maghemite (Ag–γ-Fe₂O₃) nanocomposite via a modified co-precipitation method was developed. The prepared magnetic nanocomposite was characterized by means of thermal analysis, transmission electron microscope, X-Ray diffraction, vibrating sample magnetometer and Fourier transform infrared techniques. The characterization results showed that the prepared Ag–γ-Fe₂O₃ nanocomposite is nanocrystalline and 6–8 nm in size with superparamagnetic behavior. The synthesized Ag–γ-Fe₂O₃ nanocomposite showed exceptional catalytic activities towards reduction of nitroaromatic compounds with specific activities parameters of 1441.7 and 904.2 s^??1 g_Ag^?1 for both 4-nitrophenol and 2-nitroaniline, respectively. Besides, it shows a superior activity for catalytic degradation of methyl orange. All the three catalytic reactions were carried out in aqueous medium at room temperature and in the presence of reducing agent NaBH₄. The magnetic behavior of the synthesized Ag–γ-Fe₂O₃ enables the ease of separation of the nanocomposite from the reaction medium for further reuse.

Graphical Abstract

Open image in new window

     

Effect of Field Strength and Electronegativity of CaO and MgO on Structural and Optical Properties of SiO<Subscript>2</Subscript>–K<Subscript>2</Subscript>O-CaO-MgO Glasses

The glass composition 55 SiO₂-10 K₂O-(35-x) CaO-(x) MgO (0 ≤ x ≤ 30) is prepared by the melt quenched technique. The as prepared samples are characterized by X-ray diffraction, Fourier Transform-Infrared Spectroscopy (FT-IR) and UV-Visible reflectance spectroscopy. The MgO containing glasses show better polymerization (cross-linking) and have a compact glass network as compared to CaO containing glass. Interestingly, some weak bonds are observed around 1393, 1461 and 1530 cm^-1 in FT-IR spectra related to Ca/Mg-O-H. The optical band gap of the series varies from 3.42 eV to 3.72 eV, indicating wide-band gap materials that could be used in non-linear optical applications.     

Vitreous region and properties of glasses of the Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>–GeS<Subscript>2</Subscript>–PbF<Subscript>2</Subscript> system

Vitrification in the Ga₂S₃–GeS₂–PbF₂ system is considered. The physicochemical properties of glasses, such as density, microhardness, electroconductivity, refraction index, and transmission percentage of specimens in visible and IR ranges of spectrum are studied; differential thermal analysis is carried out; and Raman and electron paramagnetic resonance spectra are investigated.     

Role of CeO<Subscript>2</Subscript> in Rh/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for CO<Subscript>2</Subscript> Reforming of Methane

Abstract  

The Rh/α-Al₂O₃ catalyst was modified by CeO₂ in order to improve the thermal stability and the carbon deposition resistance during the CO₂ reforming of methane The carbon formation was determined by TPO, TEM and Raman spectroscopy. Characterization results showed that the incorporation of Ce in the support inhibits the carbon deposition, increasing the useful life and the stability of the Rh base catalysts.     

Phase equilibrium of the ternary system of NH<Subscript>4</Subscript>Cl-CaCl<Subscript>2</Subscript>-H<Subscript>2</Subscript>O at 50°C

The equilibrium data on the ternary system of NH₄Cl—CaCl₂—H₂O at 50°C were investigated using the wet-residue method. The experimental results show that there are three pure phase crystal areas of NH₄Cl, 2NH₄Cl·CaCl₂·3H₂O and CaCl·2H₂O, two mixture phase crystal areas of NH₄Cl and 2NH₄Cl·CaCl·3H₂O, and 2NH₄Cl ·CaCl₂·3H₂O and CaCl·2H₂O in the system. A new hydration double salt (2NH₄Cl·CaCl·3H₂O) was found in the ternary equilibrium system for the first time.     

Effect of preparation procedure of Iro<Subscript>2</Subscript>–Nb<Subscript>2</Subscript>o<Subscript>5</Subscript> anodes on surface and electrocatalytic properties

The influence of the electrode manufacturing procedure on surface and electrocatalytic properties for oxygen and ozone evolution at electrodes of nominal composition Ti/[IrO₂–Nb₂O₅] (45:55 mol%) was investigated. Thermal decomposition at 450 °C (1 h, air stream) was adopted as standard procedure. Metal support pretreatment, solvent mixture, method of applying the precursor mixture and calcination procedure were all investigated. X-ray diffraction, scanning electronic microscopy, voltammetric and differential capacity analysis show the use of HCl 1:1 as solvent and applying the mixture by brush led to fragile rugged/porous oxide coatings. However, for the same conditions, but controlled calcination (heating/cooling rates), the coating becomes more compact. Using isopropanol as solvent results in a more homogeneous coating, presenting the lowest morphology factor. Kinetic investigation shows the rugged/porous coating presents the lowest Tafel slopes and the highest global electrocatalytic activity for OER. The more compact the coating the lower the electrochemically active surface area and the global OER activity. Ozone efficiency depends on the electrochemically active area while support pretreatment strongly influences the lifetime of the electrode. Application of a Pt interlayer between the oxide and Ti base improves the service life.     

Enhancement of combustion of a hydrogen-air mixture by excitation of O<Subscript>2</Subscript> molecules to the <Emphasis Type="Italic">a</Emphasis><Superscript>1</Superscript>Δ<Subscript><Emphasis Type="Italic">g</Emphasis></Subscript> state

The possibility of increasing the laminar flame velocity in a hydrogen-air mixture by excitation of O₂ molecules into the a ¹Δ _g singlet state. The presence of 10% of O₂(a ¹Δ _g ) molecules in oxygen is demonstrated to result in noticeable (up to 50%) enhancement of mixture burning. The temperature of combustion products and also the concentrations of H₂O, NO, and other constituents increase. The greatest effect of O₂(a ¹Δ _g ) molecules is manifested in combustion of lean mixtures; the least pronounced effect is observed in rich mixtures. These effects are caused by intensification of the chain mechanism in the presence of a super-equilibrium amount of excited O₂(a ¹Δ _g ) molecules in a hydrogen-air mixture. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 4, pp. 3–12, July–August, 2008.     

Synthesis and study of mesoporous xerogels and nanopowders of a metastable solid solution 97ZrO<Subscript>2</Subscript>–3Y<Subscript>2</Subscript>O<Subscript>3</Subscript> for the fabrication of catalyst substrates

The—technology of the liquid-phase synthesis of metastable phases in the ZrO₂–Y₂O₃ system has been developed. Mesoporous xerogels with the specific surface area of ~350 m²/g and monophase nanopowders (5–10 nm) of the tetragonal solid solution (ZrO₂)_0.97(Y₂O₃)_0.03 have been obtained and their structural peculiarities have been revealed. The efficiency of the suggested technology and good prospects of the synthesized ZrO₂-based precursors in creating catalysts’ substrates have been demonstrated.     

Combustion chemistry of ternary blends of hydrogen and C<Subscript>1</Subscript>–C<Subscript>4</Subscript> hydrocarbons at atmospheric pressure

Interest in the combustion chemistry of multifuel blends is motivated by the need to study the combustion of natural gas, which is known to be a mixture of alkanes. The present study performed using molecular beam mass spectrometry and numerical modeling has shown that the width of the zones of hydrogen and methane consumption in the H₂/CH₄/C₃H₈/O₂/Ar flame and the width of the zones of methane and propane consumption in the CH₄/C₃H₈/C₄H₁₀/O₂/Ar flame differ significantly from each other. The causes of this phenomenon were determined by analyzing the modeling results. It has been found that in the presence of heavier compounds, lighter fuels, such as H₂ and CH₄, are formed, which reduces the total rate of their consumption and, hence expands the zone of their consumption in the flame. The influence of the presence of hydrogen in the fuel mixture on the concentration of C₂ hydrocarbons has also been studied. It has been established that the addition of hydrogen reduces the maximum concentration of ethane, ethylene, and acetylene in the flame, and the fraction of unsaturated C₂ hydrocarbons with respect to saturated ones also decreases.     

STudy of the physicomechanical properties of modified raw materials of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> – SIC – C composites based on HAC and ACPB

Results are given for a study of the dependence of apparent density and ultimate strength in compression on the quantity of silica and form of modifying addition (Al, Si, B and mixtures of them) for materials of the composition Al₂O₃ – SiC – C based on high-alumina cement and aluminochromium phosphate binder after low-temperature (400°C) heat treatment. It is established that the most efficient form the point of view of compaction and strengthening of raw material of corundum-graphite refractory is addition of aluminum powder.