Synthesis of the study of solid solutions based on the ZrO<Subscript>2</Subscript>–HfO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>(CeO<Subscript>2</Subscript>) system

The results of the studies of the conditions of the liquid-phase synthesis of highly dispersed xerogels with a low degree of agglomeration and precursor nanopowders (~10–12 nm) based on zirconium dioxide in the ZrO₂–HfO₂–Y₂O₃(CeO₂) system are presented. The thermal decomposition of xerogels and formation of crystalline solid solutions with the structure of fluorite are investigated. The optimal conditions for the solidification of nanodispersed powders for fabricating compact ceramics based on solid solutions of ZrO₂ and the physical–chemical properties of these ceramics are studied.     

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.     

Effects of the geometry and operating temperature on the stability of Ti/IrO<Subscript>2</Subscript>–SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>5</Subscript> electrodes for O<Subscript>2</Subscript> evolution

Ternary IrO₂–Sb₂O₅–SnO₂ anode has shown its superiorities over IrO₂ and many other electrocatalysts for O₂ evolution, in terms of electrochemical stability, activity and cost. The performance of IrO₂–Sb₂O₅–SnO₂ anodes is affected by its electrochemical properties and operating conditions. In this paper, the electrochemical stability and activity of the Ti/IrO₂–Sb₂O₅–SnO₂ anodes prepared with three different geometries were investigated under different operating conditions. It was found that anodes with large mean curvature have high electrochemical stability. Although increasing temperature results in a decrease in the stability of Ti/IrO₂–Sb₂O₅–SnO₂, the anode with a mean curvature of 200 m⁻¹ still shows acceptable service life even at 70 °C. This tolerance of high temperature was attributed to the thermal expansion difference between the substrate and the coating layer, the redox window for Ir(V)/Ir(IV) conversion, and the redox reversibility of Sb and Sn species in the coating layer.     

Photocatalytic Removal of 17α-Ethinyl Estradiol Using the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>4</Subscript> Photocatalyst

A series of Bi₂O₃/Bi₂O₄ composites were prepared by calcining raw materials with different NaBiO₃/KOH mass ratios. The Bi₂O₃/Bi₂O₄ photocatalysts were characterized by the various measurements and their photocatalytic performance was assessed by degradation of 17α-ethinyl estradiol (EE2). The Bi₂O₃/Bi₂O₄ photocatalysts have wider visible light absorption and lower fluorescence emission intensity than the commercial Bi₂O₃. So, they displayed superior performance in the degradation of EE2. After the adsorption equilibrium of EE2 was reached, the degradation efficiency of Bi₂O₃/Bi₂O₄ for EE2 can reach a maximum value of ~?100% in 12 min under the visible-light illumination. Degradation analysis results indicated that both holes (h⁺) and superoxide radical (·O₂^?) can affect the degradation efficiency of EE2.

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Phase relationships in the Na<Subscript>2</Subscript>ZnP<Subscript>2</Subscript>O<Subscript>7</Subscript>–LiKZnP<Subscript>2</Subscript>O<Subscript>7</Subscript> system

The phase relationships in the Na₂ZnP₂O₇–LiKZnP₂O₇ system are studied. They are represented by a mixture of the starting components in the subsolidus region. The eutectic was found at a temperature of 640°C and composition of 0.5LiKZnP₂O₇. The phase formation of this system is compared with the previously studied NaKZnP₂O₇–LiKZnP₂O₇ system. It is shown that a structural factor affects the geometry of the state diagrams.     

Vapor–Liquid Equilibrium of Binary Components of the BrCF<Subscript>2</Subscript>COOCH<Subscript>3</Subscript>–CF<Subscript>3</Subscript>COOH–BrCF<Subscript>2</Subscript>COOH–CF<Subscript>3</Subscript>COOCH<Subscript>3</Subscript> Quaternary System

Vapor–liquid equilibria of binary components of the BrCF₂COOCH₃–CF₃COOH–BrCF₂COOH–CF₃COOCH₃ quaternary system have been studied experimentally at constant pressure. The experiments have been carried out on a modified Sventoslavskii ebulliometer. Using the Aspen Plus software package, the appropriate models have been selected and the vapor–liquid equilibria for six binary systems have been simulated.     

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.     

Fe-doping effects on the structural and electrochemical properties of 0.5Li<Subscript>2</Subscript>MnO<Subscript>3</Subscript>·0.5LiMn<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>2</Subscript> electrode material

With the aim of achieving a high-performance 0.5Li₂MnO₃·0.5LiMn_0.5Ni_0.5O₂ material, a series of 0.5Li₂MnO₃·0.5LiMn _x Ni _y Fe_(1−x−y)O₂ (0.3 ≤ x ≤ 0.5, 0.4 ≤ y ≤ 0.5) samples with low Fe content was synthesized via coprecipitation of carbonates. Its crystal structure and electrochemical performance were characterized by means of powder X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, galvanostatic charge/discharge testing, cyclic voltammetry, and electrochemical impedance spectra. Rietveld refinements with a model integrating R [`3] \overline{3} m and Fm [`3] \overline{3} m indicate that a low concentration of Fe incorporated in 0.5Li₂MnO₃·0.5LiMn_0.5Ni_0.5O₂ decrease a disordered cubic domain of the composite structure. The preferential distribution of Fe in cubic rock-salt contributes to an unimaginable decrease of c-axis parameter of the predominant layered structure as the Fe content increases. Moreover, including Fe as a dopant can kinetically improve crystallization and also change the ratio of Mn³⁺/Mn⁴⁺ and Ni³⁺/Ni²⁺. As a result, 0.5Li₂MnO₃·0.5LiMn_0.4Ni_0.5Fe_0.1O₂ exhibits lower Warburg impedance and higher reversible capacity than the undoped material.     

Change of the thermal behavior of 55Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 45B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass at annealing close to the vitrification temperature

The characteristic properties of relaxation processes for 55Bi₂O₃ ? 45B₂O₃ glass were described. The pattern of changes of the vitrification temperature (T _g ) is found to be quasi-periodic; the value of the endothermic effect near T _g (ΔC’ _p ) and the difference between the softening point and the vitrification temperature (T _m –T _g ) were determined. The temperature-time parameters of the transition from quasi-periodic to the continuous change of the properties were determined and an explanation of such behavior of the system was offered.     

Thermal investigation of ammonioborite (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>[B<Subscript>15</Subscript>O<Subscript>20</Subscript>(OH)<Subscript>8</Subscript>] · 4H<Subscript>2</Subscript>O

The thermal behavior of ammonioborite (NH₄)₃[B₁₅O₂₀(OH)₈] · 4H₂O is investigated using thermal X-ray diffraction, differential thermal analysis (DTA) in air and vacuum, and thermogravimetry. It is shown that the decomposition of the mineral (dehydration, dehydroxylation, deammoniation) proceeds in several stages, and the dehydration is accompanied by the amorphization. The thermal expansion of ammonioborite is sharply anisotropic. As in the case of other hydrous pentaborates, the thermal expansion is maximum in the direction in which pentaborate groups alternate with ammonium cations.     

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.     

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.     

Structural heterogeneity of SiO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> glass

It is shown that the phase heterogeneity of SiO₂–Na₂O–Al₂O₃ glass has a liquation and crystallization nature, the balance between which is determined by the conditions of their synthesis. An increase in the aluminum oxide content decreases the number of liquation and crystallization sites, and also the linear sizes of the crystalline formations without eliminating the phase separation due to the liquation. The area of metastable immiscibility in the SiO₂–Na₂O–Al₂O₃ system, which is determined by scanning electron microscopy, is probably wider than the area detected by the optical methods.     

An Efficient Process for the Cyclization of N-β-hydroxyethyl-N-methyl-1,3-propanediamine to N-methylhomopiperazine Over Cu<Subscript>20</Subscript>Cr<Subscript>10</Subscript>Mg<Subscript>10</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Abstract  

Continuous synthesis of N-methylhomopiperazine over Cu–Cr–Mg/γ-Al₂O₃ has been developed. The doped Cr improves the dispersion of the Cu⁰ particles and inhibits the generation of CuAl₂O₄ so that the Cu⁰ particles are retained as the active sites. Doped Mg neutralizes the strong acid sites in Cu₂₀Cr₁₀Mg₁₀/γ-Al₂O₃, and led to a decrease in coking side reactions. The reaction parameters were optimized and N-methylhomopiperazine was obtained in a yield of 66%.     

Operando X-ray Absorption Spectroscopy Study of Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> During the Total Oxidation of C<Subscript>3</Subscript>H<Subscript>6</Subscript>

Operando X-ray absorption fine structure (XAFS) investigations were performed on Pt/γ-Al₂O₃ during the total oxidation of C₃H₆ in reducing and oxidizing atmospheres. Study of the Pt valance state and catalytic conversion behavior as a function of temperature revealed that both the creation of metallic Pt sites and the activation of adsorbed species on Pt are important for the functioning of the catalytic reaction at low temperature.     

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.     

Hopping Mechanism of Charge Transfer in the Thin Layers of a Ge<Subscript>28.5</Subscript>Рb<Subscript>15</Subscript>S<Subscript>56.5</Subscript> Vitreous System

The results of the study of the charge transfer processes in the thin layers of a Ge_28.5Рb₁₅S_56.5 vitreous system are presented. The power-law dependence of the conductivity on frequency and a decrease in the value of the exponent s with increasing temperature are found. The charge transfer is a thermally activated process and two areas on the temperature dependence of conductivity are present. The activation energies of these areas are Е₁ = 0.20 ± 0.01 and Е₂ = 0.50 ± 0.01 eV, respectively. The obtained results are explained within the scope of the correlated barrier hopping (CBH) model of the hopping conductivity in disordered systems. The main microparameters of the system, namely, the density of the localized state (N), hopping length (R_ω), and the maximal value of the height of the potential barrier (W_M), are calculated.     

Kinetics of Hydrolytic Polycondensation of Silicon Dioxide in the SrO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> Systems

The kinetics of polycondensation in solutions during the liquid-phase synthesis of ceramic material precursors based on a SrO–B₂O₃–SiO₂ system are studied by spectrophotometry. The ratio between the quantitative content of tetraethoxysilane and the reaction rate of the formation of polymer forms is proved.     

Effects of ZnO–B<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on sintering behaviors and microwave dielectric properties of Ba<Subscript>4</Subscript>Sm<Subscript>9.33</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript> ceramics

Effects of ZnO–B₂O₃ (ZB) addition on the densification, phase evolution and microwaves dielectric properties of Ba₄Sm_9.33Ti₁₈O₅₄ (BST) ceramics for low-temperature fired applications have been investigated. The sintering temperature of BST ceramics can be effectively lowered to about 1000°C with introduction of ZB. Tungsten bronze like single phase is observed in the BST ceramics with 0.5 and 1.0% ZB. However, Sm₂Ti₂O₇ secondary phase appears when ZB addition reaches 2%, and Sm₂Ti₂O₇ phase gradually increases with the increase ZB addition. Microwave dielectric properties of the present ceramics are strongly dependent on phase constitution and density. Optimal microwave dielectric properties of ε = 63.4, Qf = 2830 GHz, τ _f =–8.8 ppm/°C is obtained for BST ceramics with 1% ZB addition.