Highly ordered mesoporous CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript> with crystalline walls

The highly ordered mesoporous CoFe₂O₄ and CuFe₂O₄ with crystalline walls can be synthesized by hard template with using mesoporous silica SBA-15 as hard template and using ferric nitrate, cobalt nitrate, and copper nitrate as metal precursors. These new mesoporous materials above have high surface areas, narrow pore size distribution, and large pore volumes, which are believed to be valuable for the potential application in the field of sensors, catalysis, message recording, magnetics, and biology. This work provides a method to fabricate the highly ordered mesoporous materials composed of multi-metal oxides with crystalline walls. The development of such versatile approach is of great significance in practical application. It can be envisaged that this established method is significantly expandable to the controlled synthesis of the mesoporous functional materials with diverse compositions.     

Structure and properties of glasses in the MgSO<Subscript>4</Subscript>-Na<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>-KPO<Subscript>3</Subscript> system

A glass formation region has been established in the MgSO₄-Na₂B₄O₇-KPO₃ system. This region is located in the borate-phosphate part of the concentration triangle and occupies ∼40% of the triangle area. Based on the spectral data obtained (nuclear magnetic resonance, IR and Raman spectroscopy), a model is proposed in terms of which the physicochemical properties (such as the linear thermal expansion coefficient, the softening temperature, and the glass transition temperature) of the samples are discussed.     

Phase Equilibria in the Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>-SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> System

The phase equilibria are investigated and the phase diagram is constructed for the Gd₂O₃-SrAl₂O₄ pseudobinary join of the Gd₂O₃-SrO-Al₂O₃ ternary oxide system. One ternary compound, namely, Gd₂SrAl₂O₇, is revealed in the Gd₂O₃-SrAl₂O₄ join. It is found that this compound undergoes congruent melting.     

Phase equilibria in the Ho<Subscript>2</Subscript>O<Subscript>3</Subscript>-SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> system

The phase formation is investigated and the phase diagram of the Ho₂O₃-SrAl₂O₄ system is constructed. A ternary compound, namely, Ho₂SrAl₂O₇, is revealed. It is established that this compound undergoes incongruent melting.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Modification of Mg<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>5</Subscript>(OH)<Subscript>4</Subscript> nanotubes by magnetite nanoparticles

The magnetite nanoparticles and nanocomposite “Nanotube of hydrosilicate Mg—magnetite nanoparticles—Mg-ChR-NT/Fe₃O₄-NP” were obtained by coprecipitation. The composition of the synthesized samples has been established by X-ray diffraction. Using transmission electron microscopy, the presence of magnetite nanoparticles has been detected both inside the NTs and at the external surface of the NT walls. The specific surface of the NTs, nanoparticles, and composite is determined.     

Aqueous-Phase Hydrogenolysis of Glycerol to 1,3-propanediol Over Pt-H<Subscript>4</Subscript>SiW<Subscript>12</Subscript>O<Subscript>40</Subscript>/SiO<Subscript>2</Subscript>

Abstract  

Hydrogenolysis of glycerol to 1,3-propanediol in aqueous-phase was investigated over Pt-H₄SiW₁₂O₄₀/SiO₂ bi-functional catalysts with different H₄SiW₁₂O₄₀ (HSiW) loading. Among them, Pt-15HSiW/SiO₂ showed superior performance due to the good dispersion of Pt and appropriate acidity. It is found that Br?nsted acid sites facilitate to produce 1,3-PDO selectively confirmed by Py-IR. The effects of weight hourly space velocity, reaction temperature and hydrogen pressure were also examined. The optimized Pt-HSiW/SiO₂ catalyst showed a 31.4% yield of 1,3-propanediol with glycerol conversion of 81.2% at 200 °C and 6 MPa.     

Synthesis and crystal structure of the low-temperature modification of Li<Subscript>12</Subscript>Zn<Subscript>4</Subscript>(P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>5</Subscript>

The crystal structure of a low-temperature modification of the Li₁₂Zn₄(P₂O₇)₅ compound has been determined by full-profile analysis from the X-ray powder diffraction data. The compound crystallizes in the monoclinic crystal system (a = 5.130(1) Å, b = 13.454(1) Å, c = 8.205(1) Å, β = 90.36(1)°, space group P2₁/n, Z = 4) and has a framework structure in which the zinc and lithium atoms statistically occupy equivalent positions.     

Photoreduction of CO<Subscript>2</Subscript> into CH<Subscript>4</Subscript> using Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> double-layered dense films

Nano-sized bismuth sulfide (Bi₂S₃) and titanium dioxide (TiO₂) with the orthorhombic and anatase tetragonal structures, respectively, were synthesized for application as catalysts for the reduction of carbon dioxide (CO₂) to methane (CH₄). Four double-layered dense films were fabricated with different coating sequences—TiO₂ (bottom layer)/Bi₂S₃ (top layer), Bi₂S₃/TiO₂, TiO₂/Bi₂S₃: TiO₂ (1 : 1) mix, and Bi₂S₃: TiO₂ (1 : 1) mix/Bi₂S₃: TiO₂ (1 : 1) mix—and applied to the photoreduction of CO₂ to CH₄; the catalytic activity of the fabricated films was compared to that of the pure TiO₂/TiO₂ and Bi₂S₃/Bi₂S₃ doubled-layered films. The TiO₂/Bi₂S₃ double-layered film exhibited superior photocatalytic behavior, and higher CH₄ production was obtained with the TiO₂/Bi₂S₃ double-layered film than with the other films. A model of the mechanism underlying the enhanced photoactivity of the TiO₂/Bi₂S₃ double-layered film was proposed, and it was attributed in effective charge separation.     

Crystal structure of the K<Subscript>2</Subscript>(Zn<Subscript>3</Subscript>P<Subscript>4</Subscript>O<Subscript>14</Subscript>) compound

Single crystals of potassium zinc phosphate, namely, K₂(Zn₃P₄O₁₄), are grown by crystallization of a glass of the related compound. The crystal structure of the compound is determined using single-crystal X-ray diffraction.     

Combustion and structure formation in the Ti-Ta-C-Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> system

Biocompatible composites (Ti, Ta)C _x + Ca₃(PO₄)₂ for deposition of nanofilms onto load-bearing implants by ion-plasma sputtering were prepared from Ti + Ta + C + Ca₃(PO₄)₂ mixtures by forced SHS compaction. The effect of Ta + C addition to green mixtures (characterized by parameter z) on the structure/phase formation in combustion products was explored. The addition of tantalum and carbon was found to have little or no influence on the burning velocity U and combustion temperature T _c. Two thermal spikes exhibited by thermograms were associated with the occurrence of two consecutive reactions leading to formation of titanium and tantalum carbides. With increasing z, the grain size of (Ti, Ta)C was found to diminish, its relative density to decrease, while the hardness to markedly grow.      

Inexpensive synthesis of a high-performance Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> photocatalyst: Magnetic recovery and reuse

A sol-gel technique has been developed for the synthesis of a magnetite-silica-titania (Fe₃O₄-SiO₂-TiO₂) tertiary nanocomposite with improved photocatalytic properties based on the use of inexpensive titania and silica precursors. The exceptional photocatalytic activity of the resulting materials was demonstrated by using them to photocatalyze the degradation of methylene blue solution. The best formulation achieved 98% methylene blue degradation. An interesting feature of the present work was the ability to magnetically separate and reuse the catalyst. The efficiency of the catalyst remained high during two reuses. The synthesized nanomaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, ultra-violet-visible spectroscopy, diffuse reflectance spectroscopy, and thermogravimetric analysis. XRD analysis revealed the formation of multicrystalline systems of cubic magnetite and anatase titania crystals. SEM and TEM characterization revealed well-developed and homo-geneously dispersed particles of size less than 15 nm. FTIR spectra confirmed the chemical interaction of titania and silica. It was further noticed that the optical properties of the prepared materials were dependent on the relative contents of their constituent metal oxides.

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Preparation and electrochemical properties of spherical LiFePO<Subscript>4</Subscript> and LiFe<Subscript>0.9</Subscript>Mg<Subscript>0.1</Subscript>PO<Subscript>4</Subscript> cathode materials for lithium rechargeable batteries

The spherical LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C powders were successfully prepared from spherical FePO₄ via a simple uniform-phase precipitation method at normal pressure, using FeCl₃ and H₃PO₄ as the reactants. The FePO₄, LiFePO₄/C, and LiFe_0.9Mg_0.1PO₄/C powders were characterized by scanning electron microscopies (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectrometer (XPS), and tap-density testing. The uniform spherical particles produced are amorphous, but they were crystallized to FePO₄ after calcining above 400 °C. Due to the homogeneity of the basic FePO₄, the final products, LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C, are also significantly uniform and the particle size is of about 1 μm in diameter. The tap-density of the spherical LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C are 1.75 and 1.77 g cm⁻³, respectively, which are remarkably higher than the non-spherical LiFePO₄ powders (the tap-density is 1.0–1.3 g cm⁻³). The excellent specific capacities of 148 and 157 mAh g⁻¹ with a rate of 0.1 C are achieved for the LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C, respectively. Comparison of the cyclic voltammograms of LiFePO₄/C and LiFe_0.9Mg_0.1PO₄/C shows enhanced redox current and reversibility for the sample substituting Mg on the Fe site. LiFe_0.9Mg_0.1PO₄/C exhibits better high-rate and cycle performances than the un-substituted LiFePO₄/C.     

NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> Nanoparticles Stabilized by Porous Silica Shells

Abstract  

NiFe₂O₄ nanoparticles stabilized by porous silica shells (NiFe₂O₄@SiO₂) were prepared using a one-pot synthesis and characterized for their physical and chemical stability in severe environments, representative of those encountered in industrial catalytic reactors. The SiO₂ shell is porous, allowing transport of gases to and from the metal core. The shell also stabilizes NiFe₂O₄ at the nanoparticle surface: NiFe₂O₄@SiO₂ annealed at temperatures through 973 K displays evidence of surface Ni, as verified by H₂ TPD analyses. At 1,173 K, hematite forms at the surface of the metallic cores of the NiFe₂O₄@SiO₂ nanoparticles and surface Ni is no longer observed. Without the silica shell, however, even mild reduction (at 773 K) can draw Fe to the surface and eliminate surface Ni sites.     

Ni<Superscript>2+</Superscript> reduction under solar irradiation over CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/TiO<Subscript>2</Subscript> catalysts

The photo-electrochemical characterization of the hetero-system CoFe₂O₄/TiO₂ was undertaken for the Ni²⁺ reduction under solar light. The spinel CoFe₂O₄ was prepared by nitrate route at 940 °C and the optical gap (1.66 eV) was well matched to the sun spectrum. The flat band potential (-0.21 V_SCE) is more cathodic than the potential of Ni²⁺/Ni couple (-0.6 V_SCE), thus leading to a feasible nickel photoreduction. TiO₂ with a gap of 3.2 eV is used to mediate the electrons transfer. The reaction is achieved in batch configuration and is optimized with respect to Ni²⁺ concentration (30 ppm); a reduction percentage of 72% is obtained under sunlight, the Ni²⁺ reduction is strongly enhanced and follows a first order kinetic with a rate constant of 4.6×10^-2 min^-1 according to the Langmuir-Hinshelwood model.     

High-temperature crystal chemistry of α-Na<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> and β-NaB<Subscript>3</Subscript>O<Subscript>5</Subscript> layered borates

The thermal expansion of two layered sodium borates is investigated using high-temperature X-ray powder diffraction. It is established that both compounds are characterized by strong anisotropy of thermal expansion due to the hinge mechanism. Special (singular) points are revealed in the temperature dependences of the angular lattice parameters for the α-Na₂B₄O₇ compound. The temperature of manifestation of these singularities corresponds to the glass transition temperature of the melt of the same chemical composition. The assumption is made that the angular lattice parameters (angles between atomic rows) in compounds with a considerable degree of ionic bonding are more sensitive to variations in temperature as compared to the linear lattice parameters (interatomic distances). It is experimentally in situ demonstrated with high-temperature X-ray diffraction that the β-NaB₃O₅ borate is peritectically melted at a temperature of 725 ± 10°C with the formation of the α-Na₂B₈O₁₃ octaborate.     

Synthesis of spinel Ni<Subscript>0.75</Subscript>Zn<Subscript>0.25</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> and the properties of a coating obtained by gas-flame spraying

Ferrite Ni_0.75Zn_0.25Fe₂O₄ was prepared by the solid-state synthesis and thermal decomposition of the complex oxalate Ni_0.75Zn_0.25Fe₂(C₂O₄)₃ · 6H₂O. The oxalate precursor and the products obtained at different stages of the thermal decomposition were identified by differential thermal analysis and X-ray and X-ray photoelectron spectroscopy. The properties of a ferromagnetic coating deposited on a substrate by gasflame coating were studied. The magnetic properties of the Ni-Zn ferrite product and the ferromagnetic coating were also investigated.     

Structure and electrical conductivity of glasses in the Na<Subscript>2</Subscript>O-Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> system

The temperature-concentration dependence of the electrical conductivity of glasses in the Na₂SO₄-NaPO₃ and Na₂O-P₂O₅ systems has been investigated. Based on the obtained experimental data (IR spectra, density, microhardness, sound velocity, and paper chromatography), it has been demonstrated that SO₄²⁻ ions form terminal groups through the incorporation into polyphosphate fragments of the structure of glasses in the Na₂SO₄-NaPO₃ system. An increase in the electrical conductivity of glasses in this system by a factor of ∼1000 (as compared to NaPO₃) at 25°C and a decrease in the activation energy for electrical conduction from 1.40 to 1.10 eV have been interpreted from the viewpoint of the decrease in the dissociation energy E _d of polar sulfate phosphate structural chemical fragments formed in the glass bulk upon introduction into sodium metaphosphate Na₂SO₄. This leads to an increase in the number of dissociated sodium ions, which are charge carriers, and to a decrease in the energy (E _a) of their activation shift in the sublattice formed by sulfate phosphate fragments of the structure.     

Physicochemical and optical properties of glasses in the Ga<Subscript>4</Subscript>Ge<Subscript>21</Subscript>Se<Subscript>50</Subscript>-Sb<Subscript>2</Subscript>Se<Subscript>3</Subscript> system

This paper reports on the results of an investigation into the concentration behavior of the glass-forming ability, heat resistance, glass transition temperature, density, refractive index, transparent spectral region, and impurity optical absorption of glasses in the Ga₄Ge₂₁Se₅₀-Sb₂Se₃ system. The data obtained indicate that glasses in the Ga₄Ge₂₁Se₅₀-Sb₂Se₃ system with a high Sb₂Se₃ content are of interest as materials for use in fiber optics.