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.     

An Efficient and Eco-friendly MoO<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> Solid Acid Catalyst for Electrophilic Aromatic Nitration with N<Subscript>2</Subscript>O<Subscript>5</Subscript>

Abstract  

Electrophilic aromatic nitration using N₂O₅ as a green nitrating agent catalyzed by MoO₃–SiO₂ under mild conditions has been described. A series of MoO₃–SiO₂ catalysts with varying MoO₃ loadings (5–20 mol%) were prepared by sol–gel technique and characterized using FTIR, XRD, SEM, BET and NH₃–TPD to study its surface properties. MoO₃–SiO₂ shows good catalytic activity and reusability for the nitration of alkyl and halogen aromatics giving high conversions, but less efficiency for the deactivated aromatics. Reactions conducted under non-acidic conditions using N₂O₅ makes the process safe and environmentally friendly.     

Photon interaction parameters for some ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Some photon interaction parameters such as mass attenuation coefficient, effective atomic number, half value layer, mean free path and electron density for 15ZnO–(17.5–x)Al₂O₃–xFe₂O₃–67.5P₂O₅ glass system (x = 0, 7.5, 12.5, 17.5) and 15ZnO–(25–x)Al₂O₃–xFe₂O₃–60P₂O₅ glass system (x = 0, 25) have been investigated in the photon energy range of 1 keV to 100 GeV. It has been observed that all the photon interaction parameters for the selected glass systems vary with the photon energy. Among the selected glass systems, the sample 15ZnO–25Fe₂O₃–60P₂O₅ glass system shows maximum values for mass attenuation coefficients, effective atomic numbers, electron densities and minimum values for mean free path and half value layer in the entire energy grid.     

Hydroisomerization of Benzene-Containing Gasoline Fraction on Pt/B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pt/WO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

The effect of the hydroisomerization conditions of the benzene-containing fraction of catalytic reforming gasoline on the yield and composition of products is studied on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts. These catalysts allow benzene to be completely removed from the raw material. At the same time, the greatest yields of liquid products are obtained with minimal losses of the octane number at 2 MPa, a mass feedstock hourly space velocity (MFHSV) of 2 h^?1, and 325°C: 96.3 and 95.4 wt % on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts, respectively. The activity of the catalysts is maintained for 100 h during their operation.     

Mechanical,Structural and Thermal Properties of Transparent Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–TeO<Subscript>2</Subscript> Glass System

Oxide based optical glass materials has important potential material in many applications from fiber optic to sensor due to the high transparency and amourphous structures. The objective of this study is to synthesize the novel optical glass materials based on the bismuth and aluminum contents to be able to determine the physical, chemical and mechanical properties by considering the systematic experimental steps. In this study, Bi₂O₃–Al₂O₃ based tellurite optical glasses have been prepared by using conventional melt quenching method as a function of the both Bi₂O₃ and Al₂O₃ compositions. There is a strong interactions between the glass former and modifier ions that might effect on the structure and mechanical properties. During the experimental steps, thermal, structural and mechanical properties of the prepared glass materials have been determined considering the DTA/DSC, FT-IR spectroscopy, SEM and Vicker’s hardness techniques, respectively. Thermal parameters, like glass transition, T_g, onset, T_x, crystallization, T_p, and melting, T_m, temperatures were obtained by using DTA scan.     

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.

Graphical Abstract

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Ultrafast Spectroscopy and Red Emission from β-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>/β-Ga<Subscript>2</Subscript>S<Subscript>3</Subscript> Nanowires

Ultrafast pump-probe and transient photoluminescence spectroscopy were used to investigate carrier dynamics in β-Ga₂O₃ nanowires converted to β-Ga₂O₃/Ga₂S₃ under H₂S between 400 to 600 °C. The β-Ga₂O₃ nanowires exhibited broad blue emission with a lifetime of 2.4 ns which was strongly suppressed after processing at 500–600 °C giving rise to red emission centered at 680 nm with a lifetime of 19 μs. Differential absorption spectroscopy reveals that state filling occurs in states located below the conduction band edge before sulfurization, but free carrier absorption is dominant in the β-Ga₂O₃/Ga₂S₃ nanowires processed at 500 to 600 °C for probing wavelengths >500 nm related to secondary excitation of the photo-generated carriers from the mid-gap states into the conduction band of Ga₂S₃.     

Porous ceramics based on the ZrO<Subscript>2</Subscript>(Y<Subscript>2</Subscript>O<Subscript>3</Subscript>)–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system for filtration membranes

The results of the studies of the process of fabricating ceramic filtration membranes in the system ZrO₂(Y₂O₃)–Al₂O₃ are presented. The phase compositions of the precursor powders and sintered ceramics have been investigated and their porous structures have been determined. Two stages of the implementation of the technology were demonstrated: fabrication of substrates with an open porosity ranging from 20 to 47% and pore sizes in the 100–300 nm range, as well as the deposition of nanocrystalline aluminum oxide layers on them. It has been established that the pore size distribution in the membrane layer of α-Al₂O₃ is unimodal (from 30 to 100 nm).     

Physicomechanical properties of refractory Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–C materials with ACPC

A study has been made on the effects of the amount of silicon nitride and graphite on the physicomechanical properties of Al₂O₃–Si₃N₄–C composites for lining purposes. Adding 2.5–5.0 wt.% silicon nitride and 0.5 wt.% reactive alumina improves the properties, raises their apparent density, and increases the mechanical strength, while reducing the open porosity. Optimized compositions have been determined for refractory materials of Al₂O₃–Si₃N₄–C composition, and it has been found that to attain the higher values of physicomechanical properties the amount of graphite should constitute 5–10 wt.%.     

Notable Reactivity of Acetonitrile Towards Li<Subscript>2</Subscript>O<Subscript>2</Subscript>/LiO<Subscript>2</Subscript> Probed by NAP XPS During Li–O<Subscript>2</Subscript> Battery Discharge

One of the key factors responsible for the poor cycleability of Li–O₂ batteries is a formation of byproducts from irreversible reactions between electrolyte and discharge product Li₂O₂ and/or intermediate LiO₂. Among many solvents that are used as electrolyte component for Li–O₂ batteries, acetonitrile (MeCN) is believed to be relatively stable towards oxidation. Using near ambient pressure X-ray photoemission spectroscopy (NAP XPS), we characterized the reactivity of MeCN in the Li–O₂ battery. For this purpose, we designed the model electrochemical cell assembled with solid electrolyte. We discharged it first in O₂ and then exposed to MeCN vapor. Further, the discharge was carried out in O₂?+?MeCN mixture. We have demonstrated that being in contact with Li–O₂ discharge products, MeCN oxidizes. This yields species that are weakly bonded to the surface and can be easily desorbed. That’s why they cannot be detected by the conventional XPS. Our results suggest that the respective chemical process most probably does not give rise to electrode passivation but can decrease considerably the Coulombic efficiency of the battery.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>–Au and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Au Hybrid Nanorods: Layer-by-Layer Assembly Synthesis and Their Magnetic and Optical Properties

A layer-by-layer technique has been developed to synthesize FeOOH–Au hybrid nanorods that can be transformed into Fe₂O₃–Au and Fe₃O₄–Au hybrid nanorods via controllable annealing process. The homogenous deposition of Au nanoparticles onto the surface of FeOOH nanorods can be attributed to the strong electrostatic attraction between metal ions and polyelectrolyte-modified FeOOH nanorods. The annealing atmosphere controls the phase transformation from FeOOH–Au to Fe₃O₄–Au and α-Fe₂O₃–Au. Moreover, the magnetic and optical properties of as-synthesized Fe₂O₃–Au and Fe₃O₄–Au hybrid nanorods have been investigated.     

Bimetallic Pd–Cu/ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pd–Cu/ZrO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for methanol synthesis

Monometallic copper and bimetallic palladium-copper catalysts supported on ZnO–Al₂O₃ and ZrO₂–Al₂O₃ were prepared by conventional impregnation method and tested in methanol synthesis reaction under elevated pressure (3.5 MPa) in gradientless reactor at 220°C. The physicochemical properties of prepared catalytic systems were studied using BET, X-ray, TPR-H₂, TPD-NH₃ techniques. The promotion effect of palladium on catalytic activity and selectivity of copper supported catalyst in methanol synthesis reaction was proven. The highest activity of this system is explained by the Pd–Cu alloy formation.     

Synthesis and physicochemical properties of a solid oxide nanocomposite based on a ZrO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO system

A highly dispersive powder with a (ZrO₂)_0.92(Y₂O₃)_0.03(Gd₂O₃)_0.03(MgO)_0.02 composition and specific surface area of 150 m²/g has been synthesized via a method of coprecipitation of hydroxides with the subsequent cryochemical treatment of the gel. Nanoceramics based on the cubic modification of zirconium dioxide with the grain size of ~40–45 nm have been obtained. The temperature dependence of the specific electrical conductance of the nanoceramics within a temperature range of 350–870°C in air has been studied, and the ratio of the ionic and electronic parts of the conductance has been determined. Recommendations for the use of the obtained oxide nanocomposite as an electrolyte for a high-temperature fuel cell have been given.     

Conversion of 4-Methylanisole Catalyzed by Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and by Pt/SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>: Reaction Networks and Evidence of Oxygen Removal

Abstract  

The conversion of 4-methylanisole, a prototypical bio-oil compound, was catalyzed by Pt/Al₂O₃, Pt/SiO₂-Al₂O₃, or HY zeolite at 573 K and atmospheric pressure. More than a dozen products were formed with each catalyst, the most abundant being 4-methylphenol, 2,4-dimethylphenol, and 2,4,6-trimethylphenol; toluene was also a major product when the catalyst was supported platinum with H₂ as a co-reactant. 4-Methylphenol was the only methylphenol isomer formed in significant yields, which indicates that migration of the methyl group on the aromatic ring is not significant under the selected reaction conditions. The data determine approximate reaction networks including reactions forming 4-methylphenol, 2,4-dimethylphenol, and toluene as primary products. The kinetically significant reaction classes were transalkylation, observed with all three catalysts, and hydrogenolysis (including hydrodeoxygenation) and hydrogenation, observed only with the platinum-containing catalysts operating in the presence of H₂. Data such as those reported here provide a starting point for predicting the conversion of whole bio-oils for removal of oxygen and upgrading of fuel properties.     

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.     

Synthesis and Physicochemical Properties of Nanopowders and Ceramics in a CeO<Subscript>2</Subscript>–Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> System

Nanopowders with a composition of (СeO₂)_1–x(Gd₂O₃)_x (x = 0.03, 0.05, 0.07, and 0.10) are synthesized by the coprecipitation method using cryotechnologies. The coherent scattering region (CSR) of the powders is 10–14 nm and the specific surface area is 70–81 m²/g. Based on the powders, ceramic nanosized materials with CRS of 64–71 nm are obtained. The dependence of the phase composition, microstructure, and electrical transport properties of the obtained samples on the Gd₂O₃ content is established. In a CeO₂–Gd₂O₃ system, a solid solution with the composition of (CeO₂)_0.90(Gd₂O₃)_0.10 has the highest ionic conductivity with the transfer number of ions of t_i = 0.74 at a temperature of 700°C. It is shown that ceramics of this composition can be used as a solid electrolyte of intermediate-temperature fuel cells due to their physicochemical characteristics.     

Preparation and Photocatalytic Activity of an Inorganic–Organic Hybrid Photocatalyst Ag<Subscript>2</Subscript>WO<Subscript>4</Subscript>/g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>

Ag₂WO₄/g-C₃N₄ composites with different Ag₂WO₄ concentration and calcination temperature were synthesized via a mixing and heating approach. Various techniques were used to investigate the characters of the as-prepared samples, such as thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy and photoluminescence spectroscopy. The degradation of rhodamine B (20 ppm) under visible light was performed to investigate the photocatalytic activity of Ag₂WO₄/g-C₃N₄ composites. Results indicate that the Ag₂WO₄/g-C₃N₄ is actually Ag/Ag₂WO₄/g-C₃N₄ ternary system. 7.5 wt% Ag₂WO₄/g-C₃N₄ prepared at 300 °C presented the best photocatalytic performance in rhodamine B degradation. The degradation rate reaches 0.0679 min^?1, which is 3.25 times higher than the value of pure g-C₃N₄. The enhanced activity is attributed to the synergetic effect of Ag₂WO₄, g-C₃N₄ and metal Ag. Additionally, cycling experiments also proved that the Ag₂WO₄/g-C₃N₄ photocatalyst has good stability.