Unexpected cleavage of the Cpy–Cpy bond in the reaction of 2,2′-bipyridine N,N′-diimines with acetylenes

An unusual cleavage of the C_py–C_py bond in the reaction of 2,2′-bipyridine N,N′-diimine and its C-methyl substituted derivatives with acetylenes is described. The effect of the solvent on the yield of 7,7′-bipyrazolo[1,5-a]pyridine-2,2′,3,3′-tetracarboxylates and the products of cleavage of the C_py–C_py bond has been studied. The mechanism of the cleavage reaction is discussed on the basis of DFT calculations.     

Influence of the nature of molybdenum compounds on the activity of Mo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and NiMo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> hydrotreating catalysts

The influence of the nature of molybdenum compounds on the catalytic activity of sulfided NiMo/γ-Al₂O₃ catalysts was studied. The samples were prepared by impregnating the support with mixed aqueous solutions of nickel nitrate and molybdenum-containing compounds: ammonium paramolybdate and the 6-series heteropoly compounds (HPCs) ammonium 6-molybdonickelate (NiMo₆-HPC) and ammonium 6-molybdoaluminate (AlMo₆-HPC). Complexing agents (tartaric acid or a solution of NH₃) were used for stabilizing mixed aqueous ammonium paramolybdate and nickel nitrate solutions and for simultaneously producing an acidic or alkaline medium. The starting molybdenum compounds and catalysts in the oxide form were characterized using IR spectroscopy and x-ray diffraction analysis. The activity of catalysts based on NiMo₆-HPC in the hydrogenolysis of thiophene and in the hydrotreating of the diesel fraction was higher than that of catalysts based on ammonium paramolybdate: at 320°C, the degree of sulfur removal from the diesel fraction was higher by 13–16% and the average degree of hydrogenation of polycyclic aromatic hydrocarbons was higher by 14–15%. It was also found that the use of AlMo₆-HPC does not cause such an effect.     

Formation of the Co/ZrO<Subscript>2</Subscript> catalyst active phase in the Fischer—Tropsch synthesis

Thermoprogrammed reduction and X-ray powder diffraction were used to study the phase composition and specific features of the activation process of the Co/ZrO₂ catalytic system. Results of the physico-chemical studies were compared with the data on activity and selectivity of catalysts in the Fischer—Tropsch synthesis. Reducing activation of the Co/ZrO₂ catalyst with the syn-gas can be performed directly during the Fischer—Tropsch synthesis, avoiding the high-temperature step of reduction with hydrogen. The Co/ZrO₂ catalytic system can be used for the development of catalysts for the Fischer—Tropsch synthesis, which do not require a separate step of the high-temperature reduction with hydrogen.     

Photochemistry of the IrCl<Subscript>6</Subscript><Superscript>2−</Superscript> complex in aqueous solutions in the presence of the bromide anions

Laser flash photolysis (308 nm) was applied to study photochemistry of the IrCl₆ ²⁻ complex in aqueous solutions in the presence of the Br⁻ anions. The formation of the Br₂ ^·− radical anions in the reaction between the Br⁻ ion and secondary radical pair formed after the photon absorption by the initial complex was observed. The Br₂ ^·− radical anions decay both in recombination and in the reaction with the initial IrCl₆ ²⁻ complex.     

Synthesis and structure of N-arylimines of β-tellurocyclohexenals with the intramolecular coordination N → Te bonds

A series of N-arylimines of β-tellurocyclohexenals 11 have been synthesized and the molecular and crystal structures of the compounds 11a-e and also β-(dimethyltelluronium)cyclohexenal perchlorate 12 studied by X-ray crystallography. All the compounds contain strong intramolecular coordination N → Te (O → Te) bonds of the hypervalent type. In 11a-e, the lengths of the N → Te bonds are within the range of 2.690-2.147 Å and are 1.0-1.5 Å shorter than the sum of the van der Waals radii of respective atoms. In the N-arylimines 11b-e with the electronegative groups attached to the tellurium center, the lengths of the N → Te bonds are very close to that characteristic of a standard covalent N-Te bond. The experimental observed geometries are well reproduced by the DFT calculations performed at B3LYP/LanL2DZ level of approximation. The energies of the intramolecular coordination N → Te bonds vary from 23 kJ mol⁻¹ for 11a to 119 kJ mol⁻¹ for 11e. The calculated energy of the O → Te bond in 12 was found to be 50 kJ mol⁻¹. The ¹²⁵Te NMR chemical shifts of compounds 11 span the wide range of 734.3-1622.4 ppm. The largest downfield ¹²⁵Te NMR chemical shifts are observed in the case of the compounds 11e, f in which the most electronegative atoms are attached to the tellurim centers.     

Molecular Tethering or Aggregation: Is the Existence of Charge‐Transfer Bands Indicative of the Formation of Blue‐Box/Tetrathiafulvalene Inclusion Complexes?

The interaction between tetrathiafulvalene and tetracation cyclobis(paraquat‐p‐phenylene) fragments—the key elements of many rotaxane systems—was investigated theoretically by using ab‐initio second‐order perturbation methods. In addition to the inclusion complex observed in the solid state, a thermodynamically stable “exterior” complex was identified. Calculation of the UV/Vis spectra for the inclusion and the exterior complexes indicated that the charge‐transfer band that is often used to predict the formation of the inclusion complexes in solution is, in reality, due to the exterior mode of complexation. These results suggest that UV/Vis spectroscopy is not a reliable method for assigning the complexation modes in TTF:BB⁴⁺ rotaxanes and related systems.     

The influence of the organolithium reagent nature on the possibility of the O→C<Subscript>sp</Subscript> migration of the R<Subscript>3</Subscript>Si group in propynes HC≡CCH<Subscript>2</Subscript>OSiR<Subscript>3</Subscript>

A possibility of the O→C_sp 1,4-migration of the R₃Si group in silyl ethers of terminal acetylenic alcohols upon treatment with organolithium reagents (RLi) was studied. In the case of 3-trimethylsilyloxypropyne, depending on the nature of RLi, the heterolysis of the Si—O bond occurs either by the action of acetylide formed as a result of deprotonation with the formation of 3-trimethylsilylprop-2-yn-1-ol trimethylsilyl ether, or by the action of the metalation agent with the formation of propargyl alcohol. The realization of the O→C_sp 1,4-migration of the Me₃Si group requires the use of mild organolithium reagents (lithium hexamethyldisilazanide and diisopropylamide). Silyl ethers having steric hindrance at the carbon atom bonded to the reaction center or around the silicon atom do not react with the studied organolithium reagents.     

Regime of superhigh reactivity of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + δ</Subscript> superconductor toward the components of air

Physicochemical features of the YBa₂Cu₃O_{6 + δ} superconductor synthesized via ceramic route and subjected to a kind of modification by long-term exposure to an atmosphere with low pH₂O have been studied by X-ray diffraction, thermal analysis, and magnetometry. The resulting material had a high degree of saturation with air components at room temperature and 30% humidity, up to 1.5 wt % in 30 days, which is not inherent in YBa₂Cu₃O_{6 + δ}.     

Rate of Generation of Ions H<Superscript>+</Superscript> and OH<Superscript>−</Superscript> at the Ion-Exchange Membrane/Dilute Solution Interface as a Function of the Current Density

Partial currents of water dissociation products through cation- and anion-exchange membranes that form thin desalination channels in electrodialyzers are measured. The investigations are performed in a broad interval of flow rates during desalination of dilute sodium chloride solutions at overlimiting currents. A water dissociation theory, which was developed for bipolar membranes, and a mass transfer theory that allows for the space charge formation at overlimiting currents are used to derive an expression, according to which the rate of generation of the H⁺ and OH^? ions is defined by the ratio of the current density to its critical value at which water starts undergoing discernible dissociation.     

Features of high-temperature behavior in NdCaCoO<Subscript>4</Subscript>—the catalyst of the partial oxidation of methane to syngas

The peculiarities of the high-temperature (373–1173 K) behavior and transport properties of NdCaCoO₄, which is a highly active and selective catalyst of the partial oxidation of methane to syngas, were considered. A relationship between its thermal and electrophysical properties and the structure and defectiveness of the oxygen sublattice was found. The electric conductivity of this compound, which is a two-dimensional analog of perovskite, was found to be almost independent of the oxygen pressure (\(p_{O_2 } = 10^{ - 4} - 1\) atm) and to increase with temperature, reaching ～100 S/cm at 1173 K. The temperature dependence of the conductivity of the n-type semiconductor NdCaCoO₄ has two thermoactivation regions (373–573 and 573–873 K), in which the activation energy is almost doubled (0.46 and 0.81 eV, respectively). The discovered tendencies that determine the unique catalytic properties of this material are probably due to the change in the energy spectrum of this compound. The hypothetical reasons for this change are discussed.     

Effects of TiO<Subscript>2</Subscript> on the hydrophilicity of сotton/polyester (50/50) blend fabric under UV irradiation

Alkaline TiO₂ nanoparticles treated cotton/polyester (50/50) blend fabric were prepared, and then exposed to UV irradiation. It was found that the addition of a small amount of TiO₂ nanoparticles to the coating solution improves the hydrophilicity and mechanical strength of the fabrics. The treated fabrics exhibited high water absorption as well as better hydrophilicity compared to the untreated sample. Compared to the surface of untreated blend fabric, scanning electron microscopy showed that the surface of the modified blend fabric becomes rough and covered by a layer of other materials. Furthermore, X-ray diffraction demonstrated the formation of crystalline material. In addition, thermograms showed that the modification process improved the thermostability of blend fabric.     

Study of the effect of methods for liquid-phase synthesis of nanopowders on the structure and physicochemical properties of ceramics in the CeO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Two alternative chemical synthesis methods—cryotechnological coprecipitation of hydroxides and cocrystallization of salts—were used for preparing (CeO₂)_1–x (Y₂O₃) _x nanopowders (x = 0.10, 0.15, 0.20) with a mean coherent scattering domain size of ~7–11 nm and S _sp = 2.1–97.5 m²/g. From these nanopowders, ceramic nanomaterials with mean coherent scattering domain sizes of ~61–85 nm were synthesized. It was studied how the phase composition, microstructure, and electrical transport properties of the produced samples depend on the Y₂O₃ content of a CeO₂-based solid solution and on the synthesis method. It was shown that, in the series (CeO₂)_1–x (Y₂O₃) _x (x = 0.10, 0.15, 0.20), the solid solution (CeO₂)_0.90(Y₂O₃)_0.10 has the highest ionic conductivity with the ion transport number t _i = 0.73 (600°C). In its physicochemical characteristics, this ceramic can be used as a solid electrolyte of intermediate-temperature fuel cells.     

Thermogravimetric study of the reduction of CuO–WO<Subscript>3</Subscript> oxide mixtures in the entire range of molar ratios

The present study reports the results of investigation on the role of metakaolin in the formation of ettringite in a model relevant to Portland cement. The model consists of ternary system (Trio) metakaolin–lime–gypsum. Five samples of defined ternary system were cured at different temperatures 20, 30, 40, 50 and 60 °C. Conduction calorimeter TAM AIR was mainly used to capture heat evolution at different temperatures. Thermoanalytical (simultaneous TGA/DSC) and X-ray diffraction methods were used to identify different products after curing. It results that ettringite is the main hydration product supplemented by calcium silicate and calcium aluminosilicate hydrates according to sample composition. The mechanism and kinetics of hydration, as displayed by calorimetric curves, depend on composition of samples and curing temperatures. Two main types of processes have been elucidated: reaction of aluminum ions with sulfate ones in the presence of calcium ions in aqueous solution to form ettringite supplemented by pozzolanic activity leading to the formation of calcium silicate and calcium aluminosilicate hydrates. Concomitant condensation of alumina and silica species and carbonation have influenced the course of hydration. Activation energy E _a depends slightly on composition of ternary system.     

Selective deoxygenation of vegetable oils in the presence of Pt–Sn/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

We studied deoxygenation of individual fatty esters and fatty acid triglycerides from vegetable oils and lipid extracts from microalgae in the presence of catalysts prepared by deposition of Pt–Sn-containing compounds onto the γ-aluminum oxide surface. Using individual esters as an example, selective reduction of oxygen into water was demonstrated for the first time to proceed on a catalytic system at the 5 : 1 molar ratio of Sn and Pt active components to afford hydrocarbon components of substrates in virtually quantitative yield. Transformation of vegetable oil in the presence of this catalyst affords the C₃–C₁₈ hydrocarbon fraction in yield up to 99% at the content of C₃ and C₁₈ hydrocarbons up to 90%. The fraction of C₁ and C₂ hydrocarbons and carbon oxides is not higher than 0.5%. The possibility of carbon weight loss minimization during transformation of lipids was shown for the first time.     

Mechanochemical Activation of Cu–CeO<Subscript>2</Subscript> Mixture as a Promising Technique for the Solid-State Synthesis of Catalysts for the Selective Oxidation of CO in the Presence of H<Subscript>2</Subscript>

A new ecologically clean method for the solid-phase synthesis of oxide copper–ceria catalysts with the use of the mechanochemical activation of a mixture of Cu powder (8 wt %) with CeO₂ was developed. It was established that metallic copper was oxidized by oxygen from CeO₂ in the course of mechanochemical activation. The intensity of a signal due to metallic Cu in the X-ray diffraction analysis spectra decreased with the duration of mechanochemical activation. The Cu¹⁺, Cu²⁺, and Ce³⁺ ions were detected on the sample surface by X-ray photoelectron spectroscopy. The application of temperature-programmed reduction (TPR) made it possible to detect two active oxygen species in the reaction of CO oxidation in the regions of 190 and 210–220°C by a TPR-H₂ method and in the regions of 150 and 180–190°C by a TPR-CO method. It is likely that the former species occurred in the catalytically active nanocomposite surface structures containing Cu–O–Ce bonds, whereas the latter occurred in the finely dispersed particles of CuO on the surface of CeO₂. The maximum conversion of CO (98%, 165°C) reached by the mechanochemical activation of the sample for 60 min was almost the same as conversion on a supported CuO/CeO₂ catalyst.     

Formation of the center of ignition in a CH<Subscript>3</Subscript>Cl–Cl<Subscript>2</Subscript> mixture under the action of UV light

The dependence of temperature on time is investigated using a microthermocouple at different distances from a UV light source in a mixture of chlorine and chloromethane. These relationships give an idea of the size and location of a center of photoignition. It is found that if the size of the reaction vessel in the direction of the luminous flux is much greater than the dimensions of the ignition center, the thermal expansion of a reacting gas mixture has a huge impact on such photoignition parameters as the critical concentration limits and the critical intensity of UV radiation. It is found that by increasing the length of the vessel, some chlorinated combustible mixtures lose the ability to ignite when exposed to UV light.     

Effect of the sequence of chemical transformations on the spatial segregation of components and formation of periclase-spinel nanopowders in the MgO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–H<Subscript>2</Subscript>O System

Specific features of the process in which oxide nanopowders are formed in a hydrothermal treatment of coprecipitated magnesium and iron oxides were studied. It was shown that the rate at which oxide nanoparticles are formed increases when reagents structurally close to the final product are used. It was found that, with the hydrothermal treatment of coprecipitated magnesium and iron hydroxides at 450°C combined with the subsequent thermal treatment in air at temperatures of 400–600°C, it is possible to obtain a homogeneous mixture of nanocrystalline powders based on an iron-containing spinel phase and magnesium oxide.     

Molecular dynamics simulation of the key characteristics of the supercritical CO<Subscript>2</Subscript>–pentaerythritol tetraacetate system

Supercritical CO₂ is widely used in many fields of industry. Investigation of statistical mechanics of CO₂ fluid under quasi critical and supercritical state has great significance. Equilibrium molecular dynamics (EMD) simulations are carried out to investigate the statistical mechanics and macroscopic performance of CO₂ fluid under the quasi critical and supercritical state. The results show that the bond length and bond angle distributions for supercritical CO₂ are Gaussian distribution basically. The dimers’ proportion of supercritical CO₂ system changes with pressure increasing. T-type dimer has high share within the system when pressure is higher than 9MPa. It can be inferred that T-type dimer leads to CO₂ physical properties changing tempestuously under supercritical state. The effect that lubricating oil has on microstructure and heat transfer of supercritical CO₂ is also investigated in the present work. The results show the lubricating oil produces significant effect on the dimers’ structure under low pressure.     

Dependence of enthalpies of formation of the Cu<Superscript>2+</Superscript> complexes with glycinate ions on the composition of water—dimethylsulfoxide solvent

Enthalpies of the complexing reactions of copper (II) with glycinate ions in mixtures of water with dimethylsulfoxide (DMSO) containing up to 0.9 mole parts of organic component (298 K) were obtained using a titration calorimeter. It was established that upon an increase in the DMSO content, the exothermicity of complexing increases at the first and second steps of the coordination. The obtained results were analyzed from the viewpoint of the solvation approach, based on the thermodynamic characterization of all reagents. It was shown that the main origin of the increase in the exothermicity of the complexing reactions is a weakening of ligand solvation when the DMSO concentration increases.