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.     

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.     

Synthesis and comparative studies of xerogels,aerogels, and powders based on the ZrO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–СeO<Subscript>2</Subscript> system

The technology of liquid-phase synthesis of mesoporous xerogels and aerogels based on ZrO₂–Y₂O₃–CeO₂ is developed. Xerogels are obtained by the coprecipitation of hydroxides, while aerogels are obtained in accordance with the sol–gel technology: the average pore size is 1.5–17.2 nm and the specific surface area is 120–878 m²/g. Aerogels are characterized by a high degree of porosity: the pore volume attains 1–4 cm³/g. Based on precursor xerogels, nanopowders of a tetragonal solid solution of the (ZrО₂)_0.92(Y₂О₃)_0.03(CeО₂)_0.05 composition with a particle size of 5–9 nm and S _spec = 74 m²/g were fabricated. Due to the high values of their specific surface area, the synthesized xerogels and aerogels are promising as sorbents, catalysts, or catalyst supports.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Study on flame structures and emissions of CO and NO in Various CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript>–O<Subscript>2</Subscript>/N<Subscript>2</Subscript> counterflow premixed flames

An oxygen-diluted partially premixed/oxygen-enriched supplemental combustion (ODPP/OESC) counterflow flame is studied in this paper. Flame images are obtained through experiments and numerical simulations with the GRI-Mech 3.0 chemistry. The oxygen dilution effects are revealed by comparing the flame structures and emissions with those of a premixed flame and partially premixed flame (PPF) at the same equivalence ratio (?_Σ = 0.95 and ? _f = 1.4). The results show that both PPF and ODPP/OESC flames have distinct double flame structures; however, the location of the premixed combustion zone and the distance between premixed/nonpremixed combustion zone are significantly different for these two cases. For the ODPP/OESC flame, the temperature in the premixed combustion zone is lower and the premixed zone itself is located farther downstream from the fuel nozzle, which leads to reduction of NO and CO emissions, as compared to those of the PPF. Therefore, by adjusting the distribution of the oxygen concentration in the premixed and nonpremixed combustion zones, the ODPP/OESC can effectively balance the chemical reaction rate in the entire combustion zone and, consequently, reduce emissions.     

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.     

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.     

Speciation and Electronic Structure of La<Subscript>1−x</Subscript>Sr<Subscript>x</Subscript>CoO<Subscript>3−δ</Subscript> During Oxygen Electrolysis

Cobalt-containing perovskite oxides are promising electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolyzers. However, a lack of fundamental understanding of oxide surfaces impedes rational catalyst design for improved activity and stability. We couple electrochemical studies of epitaxial La_1?xSr_xCoO_3?δ films with in situ and operando ambient pressure X-ray photoelectron spectroscopy to investigate the surface stoichiometry, adsorbates, and electronic structure. In situ investigations spanning electrode compositions in a humid environment indicate that hydroxyl and carbonate affinity increase with Sr content, leading to an increase in binding energy of metal core levels and the valence band edge from the formation of a surface dipole. The maximum in hydroxylation at 40% Sr is commensurate with the highest OER activity, where activity scales with greater hole carrier concentration and mobility. Operando measurements of the 20% Sr-doped oxide in alkaline electrolyte indicate that the surface stoichiometry remains constant during OER, supporting the idea that the oxide electrocatalyst is stable and behaves as a metal, with the voltage drop confined to the electrolyte. Furthermore, hydroxyl and carbonate species are present on the electrode surface even under oxidizing conditions, and may impact the availability of active sites or the binding strength of adsorbed intermediates via adsorbate–adsorbate interactions. For covalent oxides with facile charge transfer kinetics, the accumulation of hydroxyl species with oxidative potentials suggests the rate of reaction could be limited by proton transfer kinetics. This operando insight will help guide modeling of self-consistent oxide electrocatalysts, and highlights the potential importance of carbonates in oxygen electrocatalysis.     

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.     

Correlation of thermal properties and electrical conductivity of La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>Cu<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3−δ</Subscript> material for solid oxide fuel cells

A copper-doped ferrite with the chemical composition La_0.7Sr_0.3Cu_0.2Fe_0.8O_3−δ (LaSrCuFe) was prepared using the classical ceramics method starting from the oxides. The linear thermal expansion coefficient in air was measured in the temperature range between 550 and 1,250 K to be between 10 × 10⁻⁶ and 15 × 10⁻⁶ K⁻¹. The electrical conductivity in air was found to be higher than 100 S cm⁻¹ for temperatures lower than 1,100 K. A change of oxygen stoichiometry was found above 650 K in an atmosphere of 20 vol% oxygen with argon. This change can be correlated with the electrical conductivity.     

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.     

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.