Preparation and application of zeolite beta with super-low SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratio

This paper presents the direct synthesis of super-low SiO₂/Al₂O₃ ratio zeolite beta molecular sieve through a novel route, by which some of aluminium species are added during crystaling process. The IR results show that with the increase of aluminium content in the framework, the frequency of the band in the range of framework vibration (1060–1090 cm⁻¹) shifts to the lower wave-number; the BET surface-area decreases and the basicity of zeolite becomes stronger. In a second step, new adsorbents were obtained by solid-state ion exchanging zeolite beta with Cu(I), Ag(I) cations. The deep-desulfurization (sulfur levels of <1 ppmw) tests were performed using fixed-bed adsorption technique, the sulfur content of the treated and untreated gasoline was analyzed by microcoulometry. The experimental results show that the desulfurization performance of sorbents decreases in order: Cu(I)beta > Ag(I)beta > Na-beta. The best sorbent, Cu(I)beta, has breakthrough adsorption capacities of 0.236 mmolS/g of sorbent for model gasoline.     

Synthesis of freestanding HfO<Subscript>2</Subscript> nanostructures

Two new methods for synthesizing nanostructured HfO₂ have been developed. The first method entails exposing HfTe₂ powders to air. This simple process resulted in the formation of nanometer scale crystallites of HfO₂. The second method involved a two-step heating process by which macroscopic, freestanding nanosheets of HfO₂ were formed as a byproduct during the synthesis of HfTe₂. These highly two-dimensional sheets had side lengths measuring up to several millimeters and were stable enough to be manipulated with tweezers and other instruments. The thickness of the sheets ranged from a few to a few hundred nanometers. The thinnest sheets appeared transparent when viewed in a scanning electron microscope. It was found that the presence of Mn enhanced the formation of HfO₂ by exposure to ambient conditions and was necessary for the formation of the large scale nanosheets. These results present new routes to create freestanding nanostructured hafnium dioxide.     

Unexpected Support Effect in Hydrotreating: Evidence of a Metallic Character for ReS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and ReS<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Catalysts

Abstract  

Rhenium sulfide based catalysts were prepared by the incipient wetness impregnation method over alumina and silica supports and evaluated for 4,6-dimethyldibenzothiophene hydrodesulfurization in a high-pressure stirred-tank reactor. The catalyst prepared over silica was about six times more active for hydrodesulfurization than the corresponding catalyst prepared over alumina and a NiMo/Al₂O₃ industrial reference catalyst. This surprising and positive SiO₂ support effect was explained by a metallic character of the supported sulfide, which was demonstrated using a kinetic approach of competitive hydrogenations and by XPS characterization.     

Controllable synthesis of EU-1 molecular sieve with high SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratios in thermodynamic stable sol system

A new green chemical route was designed in this paper for the synthesis of high-silica EU-1 molecular sieve in TEAOH–SiO₂–Al₂O₃–HMBr₂–H₂O system in which tetraethylammonium hydroxide (TEAOH) substituted for sodium hydroxide (NaOH) as an alkali source. The physicochemical properties of the synthesized samples characterized by such means as X-ray powder diffraction (XRD), electrophoresis apparatus, precise pH meter, scanning electron microscope, Fourier infrared spectrometer (FT-IR), thermo gravimetric analyzer (TG) and temperature programmed desorption (NH₃-TPD). The research results showed that the SiO₂/Al₂O₃ ratio of EU-1 molecular sieve could reach 706 with TEAOH as an alkali source. The SiO₂/Al₂O₃ ratio of the product was improved greatly to 1046 with the template agent increasing. The new synthetic route has also significantly expanded the synthetic phase region. The absolute value of zeta potential of the TEAOH sol system was obviously higher than that of the NaOH sol system, indicating the thermodynamic stability of the former sol system was higher and better for the synthesis of pure high-silica EU-1 molecular sieve. The FT-IR spectra and TG/DTG diagrams of products indicated that TEA⁺ occluded in the final products could balance electronegative framework. The amount of strong, weak and the total acidity reduced with the increase of SiO₂/Al₂O₃ ratio. The catalytic results of methanol-to-hydrocarbon demonstrated that the molecular sieve prepared by the new method has better catalytic performance.     

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.     

ZrO<Subscript>2</Subscript>-and HfO<Subscript>2</Subscript>-based electrochemical sensors intended for investigation of glass-forming oxide melts

A theoretical analysis was made of the possible use of solid electrolytes with oxygen-ion conductivity for investigation of the relative basicity of silicate melts, and the optimum design of the electrochemical cell was chosen. Glasses in the SiO₂-Na₂O system were synthesized, and ceramic sensory membranes based on the cubic solid solution (ZrO₂)_0.92(Y₂O₃)_0.08 were prepared. An electrochemical cell based on ZrO₂ and HfO₂ and intended for investigation of glass-forming melts with the use of a platinum electrode and a reference electrode with oxygen-ion conductivity was designed and fabricated. The concentration dependence of the electromotive force of the electrochemical cells was examined for melts in the SiO₂-Na₂O system containing alkali oxide in different concentrations. A mathematical treatment of the obtained dependence of the electromotive force on the Na₂O concentration in this system was performed. The results obtained were used to calculate the relative oxygen ion activities and the corresponding pO values for alkali silicate melts under investigation.     

Optical Properties of CeO<Subscript>2</Subscript> Doped SiO<Subscript>2</Subscript>-Na<Subscript>2</Subscript>O-CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript> Glasses

Cerium oxide is one of the most important rare earth elements that is introduced into glass compositions due to its great effects on the optical properties. CeO₂ was introduced in Hench’s patented SiO₂-Na₂O-CaO-P₂O₅ glasses with different concentrations in order to study its effect on the optical behavior of this glass including optical band gap, transmittance, reflectance and refractive index and to give a complete view for the optical properties on cerium oxide-doped silicate glasses.     

Kinetics of crystal nucleation of Na<Subscript>2</Subscript>O · 2CaO · 3SiO<Subscript>2</Subscript>-based solid solutions in glasses of the Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript>—CaSiO<Subscript>3</Subscript> pseudobinary join

The kinetics of crystal nucleation is investigated in sodium calcium silicate glasses of two compositions (22.4 and 24.4 mol % Na₂O), which belong to the Na₂SiO₃—CaSiO₃ pseudobinary join and, according to the phase diagram, lie in the region of the formation of solid solutions between the compositions Na₂O · 2CaO · 3SiO₂ and Na₂O · CaO · 2SiO₂. The stationary rate of crystal nucleation of Na₂O · 2CaO · 3SiO₂-based solid solutions is measured as a function of temperature. It is shown that the maximum stationary rate of nucleation increases with an increase in the sodium oxide content in the initial glasses. The experimental data are analyzed in the framework of the classical nucleation theory.Original Russian Text Copyright © 2004 by Fizika i Khimiya Stekla, Soboleva, Yuritsyn, Ugolkov.     

Preparation of nanodisperse solid solutions based on ZrO<Subscript>2</Subscript> and HfO<Subscript>2</Subscript> from hydroperoxides

A procedure for preparing solid solutions based on zirconium and hafnium hydroperoxides is developed. This procedure is based on the coprecipitation of components in the presence of hydrogen peroxide. Amorphous nanopowders (S _sp = 80–90 m²/g, d _mean = 2–3 nm) without any indication of the agglomeration of particles are synthesized. After the decomposition of complex hydroperoxides at a temperature of 500°C, the compacted powders undergo an active sintering at a temperature of 1450°C. The particle size after heat treatment does not exceed 50 nm. As follows from the electrical and physical characteristics obtained for these materials, they can be recommended for the use as solid electrolytes and sensors of oxygen partial pressure.     

Preparation of amine-modified SiO<Subscript>2</Subscript> aerogel from rice husk ash for CO<Subscript>2</Subscript> adsorption

Amine-modified SiO₂ aerogel was prepared using 3-(aminopropyl)triethoxysilane (APTES) as the modification agent and rice husk ash as silicon source, its CO₂ adsorption performance was investigated. The amine-modified SiO₂ aerogel remains porous, the specific surface area is 654.24 m²/g, the pore volume is 2.72 cm³/g and the pore diameter is 12.38 nm. The amine-modified aerogel, whose N content is up to 3.02 mmol/g, can stay stable below the temperature of 300 °C. In the static adsorption experiment, amine-modified SiO₂ aerogel (AMSA) showed the highest CO₂ adsorption capacity of 52.40 cm³/g. A simulation was promoted to distinguish the adsorption between the physical process and chemical process. It is observed that the chemical adsorption mainly occurs at the beginning, while the physical adsorption affects the entire adsorption process. Meanwhile, AMSA also exhibits excellent CO₂ adsorption–desorption performance. The CO₂ adsorption capacity dropped less than 10 % after ten times of adsorption–desorption cycles. As a result, AMSA with rice husk ash as raw material is a promising CO₂ sorbent with high adsorption capacity and stable recycle performance and will have a broad application prospect for exhaust emission in higher temperature.     

Fischer-Tropsch synthesis on the cobalt impregnated catalyst using carbon-coated Ni/SiO<Subscript>2</Subscript>

Carbon-coated Ni/SiO₂ prepared by dry reforming of CH₄ with CO₂ was applied for the preparation of the cobalt-based Fischer-Tropsch synthesis (FTS) catalyst with 20 wt%Co to elucidate the metal-support interaction to FTS activity after carbon depositions on the Ni/SiO₂. The deposited carbons on the reforming catalyst of Ni/SiO₂, which were mainly in the form of filamentous or encapsulated carbons, largely increased CO conversion compared with the fresh Ni/SiO₂ without a significant variation of hydrocarbon distributions. The deposited carbons on the Ni/SiO₂ play an important role in increasing the reducibility of cobalt oxides due to a mitigated metal-support interaction. The enhanced catalytic activity during FTS reaction is mainly attributed to the proper modification of the Ni/SiO₂ surfaces with encapsulated carbons on the exposed nickel surfaces, which largely alters the reducibility of cobalt oxides by reducing the interaction of cobalt particles with the carbon-coated Ni/SiO₂ surfaces.     

Influences of polypropylene grafted to SiO<Subscript>2</Subscript> nanoparticles on the crystallization behavior and mechanical properties of polypropylene/SiO<Subscript>2</Subscript> nanocomposites

Influences of polypropylene (PP) grafted to SiO₂ nanoparticles (7 nm) were studied on the crystallization behavior and the mechanical properties of PP/SiO₂ nanocomposites. PP for the matrix and grafting was synthesized in order to have an identical primary structure, aiming at their co-crystallization and resulting reinforcement of filler-matrix interfaces. The grafted PP chains improved the dispersion of SiO₂, and notably accelerated nucleation in crystallization. It was plausible that the grafted chains whose one chain end was pinned to SiO₂ became nuclei of the crystallization (co-crystallization between the matrix and grafted chains), thus directly bridging between the matrix and SiO₂ nanoparticles. The Young’s modulus and tensile strength were most improved by the grafted PP chains at low filler contents such as 2.3 wt%, whose origin was attributed to effective load transfer to SiO₂ through the co-crystallization-mediated bridging.     

Thermal Behavior of Howlite,Ca<Subscript>2</Subscript>B<Subscript>5</Subscript>SiO<Subscript>9</Subscript>(OH)<Subscript>5</Subscript>

The thermal behavior of natural borosilicate howlite, Ca₂B₅SiO₉(OH)₅, is studied by the methods of high-temperature X-ray diffraction and differential thermal analysis in the temperature range of 30–1100°C. The thermal expansion is anisotropic (α_max/α_min = 3.6); the degree of anisotropy increases (α_max/α_min = 4.3) with a temperature increase up to 480°C (360–480°C).     

Preparation of hydrophobic SiO<Subscript>2</Subscript>@(TiO<Subscript>2</Subscript>/MoS<Subscript>2</Subscript>) composite film and its self-cleaning properties

TiO₂/MoS₂ composite was encapsulated by hydrophobic SiO₂ nanoparticles using a sol–gel hydrothermal method with methyltriethoxysilane (MTES), titanium tetrachloride (TiCl₄), and molybdenum disulfide (MoS₂) as raw materials. Then, a novel dual functional composite film with hydrophobicity and photocatalytic activity was fabricated on a glass substrates via the combination of polydimethylsiloxane adhesives and hydrophobic SiO₂@(TiO₂/MoS₂) composite particles. The influence of the mole ratios of MTES to TiO₂/MoS₂ (M:T) on the wettability and photocatalytic activity of the composite film was discussed. The surface morphology, chemical compositions, and hydrophobicity of the composite film on the glass substrate were investigated by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and water contact angle (water CA) measurements. The results indicated that the composite film exhibited stable superhydrophobicity and excellent photocatalytic activity for degradation of methyl orange (MO) even after five continuous cycles of photocatalytic reaction when M/T was 7:1. The water CA and degradation efficiency for MO remained at 154° and 94%, respectively. Further, the composite film showed a good non-sticking characteristic with the water sliding angle (SA) at about 4°. The SiO₂@(TiO₂/MoS₂) composite consisting of hydrophobic SiO₂ nanoparticles and TiO₂/MoS₂ heterostructure could provide synergistic effects for maintaining long-term self-cleaning performance.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

A novel hydrothermal releasing synthesis of modified SiO<Subscript>2</Subscript> material and its application in phenol removal process

A modified SiO₂ material (MSM) was successfully synthesized by using Na₂SiO₃ and a novel CO₂SM in the presence of CTAB through an innovative hydrothermal releasing treatment protocol. The MSM was systemically characterized using several techniques, including N₂ adsorption-desorption isotherm, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The CO₂SM as a platform for CO₂ capturing and releasing can be reversibly used for multiple cycles without significant loss of capabilities. The optimum conditions for the preparation of MSM were identified as follows: Na₂SiO3 concentration, 0.2mol/L; hydrothermal temperature, 120 °C; CO₂SM dosage, 6 g; CTAB concentration, 24 g/L, reaction time, 12 h. Additionally, the MSM exhibited high efficiency for the removal of phenol from aqueous solution: it showed a phenol adsorption capacity of 91.29mg/g when shaken with the aqueous phenol solution at 180 rpm for 1 h at 25 °C.     

Photocatalytic activity of metal-decorated SiO<Subscript>2</Subscript>@TiO<Subscript>2</Subscript> hybrid photocatalysts under water splitting

We report the fabrication of a metal-decorated hybrid nanocomposite with TiO₂ encapsulation (Metal/SiO₂@TiO₂, Metal=Pt or Ru) using a simple surface-modification chemical process. Metal nanoparticles capped with polyvinylpyrrolidone were successfully assembled on functionalized SiO₂ via electrostatic interactions, after which a thin layer of TiO₂ was coated on the surface by the sol-gel process to avoid agglomeration of the coated silica spheres. Transmission electron microscopy studies confirmed that the metal nanoparticles were uniformly distributed throughout the surface of the SiO₂ with a thin layer of TiO₂. In addition, X-ray diffraction was employed to ensure the crystal structure of the uniformly coated thin TiO₂ layer. Even after calcination at 500 °C, the structure remained intact, confirming high thermal stability. The photocatalytic activity of the metal-decorated SiO₂/TiO₂ nanocomposites was evaluated using the H₂ evolution reaction. The Metal/SiO₂@TiO₂ catalysts show the photocatalytic water splitting efficiency for H₂ generation (i.e., 0.14% for Pt/SiO₂@TiO₂ and 0.12% for Ru/SiO₂@TiO₂), while there is no generation of H₂ on the Metal/SiO₂ without a coating layer. These results indicate that the anatase crystalline coating layer has good thermal and chemical stability and plays a significant role in photocatalytic H₂ production.     

Fusion-Cast High-Chrome Refractories Synthesized in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> - MgO - SiO<Subscript>2</Subscript> System

The synthesis and comprehensive study of fusion-cast refractories based on the Cr₂O₃ - MgO - SiO₂ system containing more than 60% Cr₂O₃ are reported. Analyzed by x-ray diffractometry and petrography, the synthesized materials display a phase composition represented by a complex spinel and escolaite. Tested for stability by molten alkali-free borosilicate E-glass, the synthesized refractories are shown to be not inferior in corrosion resistance to a chromium oxide-based ceramic refractory. __________ Translated from Novye Ogneupory, No. 10, pp. 68 – 74, October, 2005.