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.     

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.     

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.     

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.     

Magneto Optical Properties of FeB<Subscript>x</Subscript>Fe<Subscript>2−x</Subscript>O<Subscript>4</Subscript> Nanoparticles

In this study, FeB_xFe_2?xO₄ nanoparticles (NPs) were synthesized by the polyol method. The M–H hysteresis curves exhibit superparamagnetic characteristics that are both coercivity and remanent magnetization values are negligible. The particle size dependent Langevin function was applied to calculate the magnetic particle dimensions around 9 nm. The measured magnetic moments of NPs are in range of (1.52–2.2) µ_B and almost half or less with respect to 4 µ_B of bulk Fe ferrite. Magnetic anisotropy was specified as uniaxial and calculated effective anisotropy constants (K _eff ) are between 43.3 × 10⁴ and 19.4 × 10⁴ emu/g. The UV–Vis diffuse reflectance spectroscopy and Kubelka–Munk theory were used to determine the optical properties. The estimated optical band gap values (2.15–2.48 eV) of FeB_xFe_2?xO₄ NPs are bigger with respect to reported values (1.88–2.12 eV) for Fe₃O₄ NPs in the literature. The bigger E _g values are mainly attributed to B concentration and partly to quantum confinement effect.     

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.     

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.     

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.     

Catalytic activation of C<Subscript>1</Subscript>—C<Subscript>3</Subscript> alkanes

The conversion of CH₄ and the C₆H₆—C₃H₈ mixture over (M, ReO _x )/Al₂O₃ (M = Ni, Co, Pt) analogues of industrial low-octane gasoline reforming catalysts containing 0.5 wt % M in a finely divided state and 0.3–1.0 wt % Re is reported. The unreduced catalysts activate the conversion of CH₄ into C₆H₆ at 650°C. Using (M, ReO _x )/Al₂O₃ + HZ catalytic mixtures (HZ = H-form of zeolite Y, M, or ZSM-5), it is possible to carry out low-temperature C₆H₆ alkylation or C₃H₈ dehydrogenation at 180–350°C. These processes are aimed at involving oil refining waste into obtaining valuable hydrocarbons. The processes can be commercial- ized at low-octane reforming and gas-phase benzene alkylation plants and can be intensified by separating the resulting H₂ in membrane reactors.     

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.     

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.     

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.     

Synthesis of magnetically separable core–shell structured Ni<Subscript>x</Subscript>Fe<Subscript>1−x</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>@TiO<Subscript>2</Subscript> nanoparticles photocatalysts for the degradation of organic dyes

In this paper, the core–shell structured NiFe₂O₄@TiO₂ nanoparticles and nanochains as photocatalysts were successfully prepared through hydrothermal and hydrolysis method. The as-prepared core–shell structure was composed of a magnetic NiFe₂O₄ core and photocatalytic titanium oxide coating shell. SEM and TEM images characterized the morphology of NiFe₂O₄@TiO₂ nanoparticles. Moreover, the results of XRD patterns proved that the TiO₂ coating shell consisted of anatase. The VSM measurements showed that the saturation magnetization values of NiFe₂O₄ and NiFe₂O₄@TiO₂ nanoparticles was 65 and 53 emu/g, respectively. The photocatalyst of NiFe₂O₄@TiO₂ nanoparticles exhibited the outstanding recyclable performance for RhB. And, the photo_degradation ration of maintained 69 % after the photocatalyst experienced ten photocatalysis experiments, which is better than that of Fe₃O₄@TiO₂ photocatalysts.     

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.     

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.     

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.     

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.     

Magnetic Properties of FeMn<Subscript>y</Subscript>Co<Subscript>y</Subscript>Fe<Subscript>2−2y</Subscript>O<Subscript>4</Subscript>@Oleylamine Nanocomposite with Cation Distribution

In this study, oleylamine (OAm) capped FeMn_yCo_yFe_2?2yO₄ (0.0?≤?y?≤?0.4) nanocomposites (NCs) were prepared via the polyol route and the impact of bimetallic Co³⁺ and Mn³⁺ ions on the structural and magnetic properties of Fe₃O₄ was investigated. The complete characterization of FeMn_yCo_yFe_2?2yO₄@OAm NCs were done by different techniques such as XRD, SEM, TGA, FT-IR, TEM, and VSM. XRD analyses proved the successful formation of mono-phase MnFe₂O₄ spinel cubic products free from any impurity. The average crystallite sizes were calculated in the range of 9.4–26.4 nm using Sherrer’s formula. Both SEM and TEM results confirmed that products are nanoparticles like structures having spherical morphology with small agglomeration. Ms continued to decrease up to Co³⁺ and Mn³⁺ content of y?=?0.4. Although Mössbauer analysis reveals that the nanocomposites consist three magnetic sextets and superparamagnetic particles are also formed for Fe₃O₄, Co_0.2Mn_0.2Fe_2.6O₄ and Co_0.4Mn_0.4Fe_2.2O₄. Cation distributions calculation was reported that Co³⁺ ions prefer to replace Fe²⁺ ions on tetrahedral side up to all the concentration while Mn³⁺ ions prefer to replace Fe³⁺ ions on the octahedral.