Low-Temperature Synthesis of Micro–Mesoporous TiO2–SiO2 Composite Film Containing Fe–N Co-Doped Anatase Nanocrystals for Photocatalytic NO Removal

Catalysis Letters - A simple low-temperature (<?100 °C) hot-water treatment was used to synthesize Fe–N co-doped anatase nanocrystals which were uniformly dispersed...     

Microwave dielectric materials based on the MgO–SiO2–TiO2 system

Ceramics in the system MgO–SiO₂–TiO₂ were prepared by standard mixed oxide route. By adding ZnO–B₂O₃ to the starting mixtures, the firing temperature of the ceramics could be reduced to 1160 °C. Small additions of MnCO₃ and CaTiO₃ improve microwave dielectric properties leading to an increase in insulation resistance and a decrease in temperature coefficient of capacitance. By adding Co₂O₃ grain growth can be inhibited and the dielectric Qf value greatly increased. The resultant ceramic material exhibited low dielectric constant and low dielectric loss: relative permittivity (ε_r): 20±2; temperature coefficient of capacitance (τ_c): 0±30 ppm/°C; Qf: 100,000 (at 10 GHz); insulation resistance: 10¹³ Ω cm:     

The MgO–TiO2–SiO2 system: Experiments and thermodynamic assessment

Phase relations in the MgO–TiO₂–SiO₂ system have been investigated in air over a wide temperature range using the equilibration method. X-ray powder diffraction, scanning electron microscopy combined with wave length X-ray spectroscopy (SEM/EPMA), and differential thermal analysis (DTA) have been used for sample characterization. Based on the obtained experimental results, isothermal sections of the system at 1523, 1673, and 1773 K have been established. The solid-state invariant reaction MgTi₂O₅ + T-SiO₂⇋P-MgSiO₃ + TiO₂ has been detected at 1625 ± 8 K by step-wise heat treatment. A partial liquidus projection has been suggested, and the temperatures and compositions of three eutectic invariant reactions have been experimentally measured by DTA and ex-situ analysis of the sample microstructures after melting using SEM/EPMA. Considering the newly obtained experimental data, thermodynamic parameters describing the system have been thermodynamically evaluated within the CALPHAD approach.     

Physicochemical and thermo physical characterization of CaO–CaF2–SiO2 and CaO–TiO2–SiO2 based electrode coating for offshore welds

This paper investigates the physicochemical and thermo-physical properties of CaO–CaF₂–SiO₂ and CaO–TiO₂–SiO₂ based electrode coating for welding offshore structures. Twenty-one electrode coating compositions have been formulated using extreme vertices design method. The coating was crushed to powder form. The powder was characterized for weight loss, density, specific heat, enthalpy, thermal conductivity, diffusivity, and specific heat. Coating's structural analysis was done using X-Ray Diffraction and Fourier transformation. X-Ray Fluorescence, Thermogravimetric Analyzer, and Hot disc have been used to characterize the coating mixture. The regression analysis has been used to study the effect of individual constituents and their binary, tertiary interactions on the properties. The obtained output of properties has been optimized using multi-response optimization.     

Epoxidation of Allylic Alcohols with TiO2–SiO2: Hydroxy-Assisted Mechanism and Dynamic Structural Changes During Reaction

Epoxidation of allylic alcohols and cyclohexene with TBHP and titania–silica aerogels containing 1 and 5wt% TiO₂ has been studied. For the oxidation of geraniol and cyclohexenol, the regio- and diastereoselectivities and kinetic data indicate an OH-assisted mechanism involving a dative bond between the OH group and the Ti site. This mechanism is disabled in the oxidation of cyclooctenol due to steric hindrance. The moderate regio- and diastereoselectivities of the aerogels, compared with those of TS-1 and the homogeneous model Ti(OSiMe₃)₄, are attributed to the presence of non-isolated Ti sites and to a silanol-assisted mechanism, according to which model the allylic alcohol is anchored to a neighboring SiOH group instead of the Ti-peroxo complex. Kinetic analysis of the initial transient period revealed rapid catalyst restructuring during the first few turnovers. A feasible explanation is the breaking of Si–O–Ti linkages of the carefully predried aerogels by water or TBHP, resulting in active Ti sites with remarkably different catalytic properties.     

SO42−–Mn–Co–Ce supported on TiO2/SiO2 with high sulfur durability for low-temperature SCR of NO with NH3

The catalysts SO₄^2 − Mn–Co–Ce/TiO₂/SiO₂ were investigated for the low-temperature SCR of NO with NH₃ in the presence of SO₂. An excellent SO₂ durability at low temperature was obtained with the catalyst used TiO₂/SiO₂ as support and modified with SO₄^2 −. The catalyst sulfated with 0.1 mol/L H₂SO₄ solution and then calcined at 300 °C exhibited the best NO_x conversion efficiency of 99.5% at 250 °C in the presence of 50 ppm SO₂. The conversion efficiency did not decrease after repeatedly used for 8 times.     

Enhanced photocatalytic activity by tailoring the interface in TiO2–ZrTiO4 heterostructure in TiO2–ZrTiO4–SiO2 ternary system

To clarify the interfacial structural of TiO₂–ZrTiO₄ heterostructure and their function in improving the catalytic behavior, TiO₂–ZrTiO₄–SiO₂ photocatalyst with mesoporous structure, a large surface area (188.54 m²g^-1) and an appropriate band gap energy (3.06 eV) was synthesized by in-situ reaction between TiO₂ and ZrO₂ at 800 °C in TiO₂–ZrO₂–SiO₂ ternary system. The concomitant effects of loading amount of TiO₂ and calcination temperatures on the interfacial interaction, and the corresponding interfacial effects on the photodegradation performance of the catalyst were investigated. Results show that an optimal amount of TiO₂ is crucial in affecting the degree of interfacial interactions. Photocatalytic activity is significantly enhanced with the strong interfacial interaction between TiO₂ and ZrTiO₄ by forming heterojunction. A higher amount of TiO₂ and calcination temperature will lead to the decrease in BET value, increase in pore size and band gap value, as well as the coarsening and aggregation of particles which exhibit negative influence on the interfacial interaction between TiO₂ and ZrTiO₄. In the photodegradation process, the prepared catalyst with a appropriate TiO₂ molar ratio (Ti:Zr:Si, 5:1:6) exhibited a RhB-adsorption of 60.7% in dark reaction, and a degradation rate of 95% after visible light irradiation for 60 min. In addition, the probable degradation mechanism for the improvement in the degradation efficiency was discussed in detail.     

Surface and bulk crystallization in Nd2O3–Al2O3–SiO2–TiO2 glasses

Neodymium aluminosilicate (Nd₂O₃–Al₂O₃–SiO₂; NdAS) glasses have been investigated for the effect of concentration of TiO₂ on the crystallization mechanism and for the effect of surface condition on crystal growth. NdAS glasses with 0–10 wt.% TiO₂ were heat-treated for nucleation and crystal growth and were examined for phase separation and morphology of surface crystals as well as for crystal growth rate. All the glasses exhibit surface crystallization, however, the glass having 8 wt.% TiO₂ also exhibits internal crystallization after a two-stage heat treatment. Surface crystallization was dependent on the condition of the glass surface and the amount of TiO₂. The crystal growth on the cut surface was faster than on the fractured surface and the growth rate in surface increased with increasing TiO₂. The phase separation found in NdAS glasses containing above 8 wt.% TiO₂, was confirmed to be an important factor controlling the internal crystallization process in Nd₂O₃–Al₂O₃–SiO₂–TiO₂ glasses.     

Preparation and characterization of equimolar SiO2–Al2O3–TiO2 ternary aerogel beads

Crack-free mesoporous equimolar SiO₂–Al₂O₃–TiO₂ ternary aerogel beads have been synthesized and characterized. Silica sol, alumina sol, and titania sol were synthesized individually to prevent the formation of inhomogeneous structure due to the different hydrolization and polymerization rate of individual precursor. After mixing these three types of acidic sols, SiO₂–Al₂O₃–TiO₂ ternary beads were prepared by the ball dropping method. The ternary aerogel beads were typically mesoporous, showing high surface area (305 m² g^?1), large pore volume (1.32 cm³ g^?1), and high surface acid amount (0.884 mmol NH₃ g^?1). Moreover, the acid sites of the ternary aerogel beads showed higher thermal stability than those of binary aerogel beads. Gradient drying (GD), supercritical drying (SD), ambient drying (AD), extended aging (EA) and hydrophobic modifying drying (HM) have been employed to investigate the effects of drying method on the characteristics of the aerogel beads. The surface areas of the ternary aerogel beads obtained by different drying methods decrease in the sequence EA > HM > GD > SD > AD. The ternary aerogel beads have been characterized by scanning electron microscopy, nitrogen adsorption, X-ray powder diffraction, Fourier-transform infrared spectroscopy (FTIR), solid-state NMR, temperature-programmed desorption measurements, pyridine adsorption FTIR, and differential scanning calorimetry.     

Fabrication of superhydrophilic self-cleaning SiO2–TiO2 coating and its photocatalytic performance

Generally, superhydrophilic self-cleaning coatings are prepared from semiconductors with photocatalytic properties. Organic pollutants attached to the coating surface can be degraded by its photocatalytic performance realizing a self-cleaning goal. Herein, SiO₂–TiO₂ composite particles were fabricated by the hydrolysis and precipitation of TiOSO₄, and SiO₂ microspheres were chosen as carriers, which are inexpensive and environmentally friendly. Then, superhydrophilic self-cleaning SiO₂–TiO₂ coatings were fabricated by spraying the composites on the surfaces of substrates. The morphology, structure and self-cleaning performance of the SiO₂–TiO₂ coating were characterized and tested. The results revealed that nano-TiO₂ was loaded on the surfaces of SiO₂ microspheres uniformly forming a hierarchical micro/nanostructure. The SiO₂–TiO₂ composite particles exhibited excellent photocatalytic degradation performance, and the degradation rate of methyl orange (10 ppm) was more than 98% under UV irradiation for 40 min. Furthermore, the coating prepared with the SiO₂–TiO₂ composite particles exhibited superhydrophilicity. A water droplet spreads completely on the coating surface in 0.35 s, and the contact angle reaches 0°. In addition, rhodamine B (RhB) and methylene blue (MB) on the coating surface can be degraded efficiently under sunlight irradiation. The SiO₂–TiO₂ composite particles can be sprayed directly on the surfaces of concrete, brick, wood, and glass slides. Therefore, the particles showed good adaptability to different substrates. The superhydrophilic property was due to the hydrophilicity of SiO₂ and TiO₂, the hierarchical micro/nanostructure of the SiO₂–TiO₂ composites, and the photoinduced superhydrophilicity of TiO₂. The above experimental results show that the as-prepared superhydrophilic self-cleaning SiO₂–TiO₂ coating has a large application potential.     

SiO2对TiO2薄膜性能的影响

采用溶胶-凝胶法分别制备出SiO2溶胶和TiO2溶胶,以不同的比例进行混胶。用旋涂法在载玻片上进行制膜。借助于紫外-可见光吸收光谱、原子力显微镜分析了SiO2/TiO2薄膜吸光性能和显微结构。通过对金黄葡萄菌和大肠杆菌的杀菌实验表明其杀菌率达99%以上。     

1250°C liquidus for the CaO–MgO–SiO2–Al2O3–TiO2 system in air

Ti-bearing blast furnace slags have been regarded as an important secondary material in modern society, and the efficient recycling of Ti oxides from it is of key interest. For this reason, more thermodynamic data is needed regarding the phase relations in different composition ranges and sections. Therefore, the equilibrium phase relations of CaO–MgO–SiO₂–Al₂O₃–TiO₂ system in a low w(CaO)/w(SiO₂) ratio of 0.6–0.8 at 1250 °C in air and fixed concentrations of MgO and Al₂O₃, were investigated experimentally using a high temperature equilibration and quenching method followed by SEM-EDS (Scanning Electron Microscope and Energy Dispersive X-ray Spectrometer) analyses. The equilibrium solid phases of perovskite (CaO·TiO₂), a pseudo-brookite solid solution (MgO·2TiO₂, Al₂O₃·TiO₂)_ss, and anorthite (CaO·Al₂O₃·2SiO₂) were found to coexist with the liquid phase at 1250 °C. The calculated results of Factsage and MTDATA were used for comparisons, and significant discrepancies were found between predictions and the experimental results. The 1250 °C isotherm has been constructed and projected on the CaO–SiO₂–TiO₂-8 wt.% MgO-14 wt% Al₂O₃ quasi-ternary plane of the phase diagram. The obtained results provide new fundamental data for Ti-bearing slag recycling processes, and they add new experimental features for thermodynamic modeling of the high-order titanium oxide-containing systems.     

Synthesis of TS-1 by microwave heating of template-impregnated SiO2–TiO2 xerogels

TS-1 was prepared by microwave heating of a SiO₂–TiO₂ xerogel dry-impregnated with the template, TPAOH. A highly crystalline product was obtained within 30 min after microwave irradiation with yields over 90%. These are significant advantages over the TS-1 obtained by conventional oven heating using alkoxide precursors in liquid phase, which requires 1–2 day crystallization time with low product yields. Characterization of the TS-1 obtained was carried out using XRD, SEM, FT-IR, and UV-vis spectroscopy, and catalytic activity was examined for 1-hexene epoxidation using H₂O₂ as oxidant. These studies revealed that the material obtained by microwave heating of the mixed oxide gel shows essentially identical physicochemical properties to those prepared by conventional means.     

Fabrication of multilayer porous structured TiO2–ZrTiO4–SiO2 heterostructure towards enhanced photo-degradation activities

Multilayer porous structured TiO₂–ZrTiO₄–SiO₂ photocatalyst with built-in TiO₂/ZrTiO₄ heterojunction and oxygen vacancies was synthesized by sol-gel method combined with template method using colloidal polystyrene spheres as templates. Results show that the multilayer porous structure can be fabricated by controlling the calcination system and the amount of template, and the fabrication of which can also contribute to the generation of oxygen vacancies by creating an anoxic environment. During the photodegradation process, high efficiency of visible light utilization can be achieved due to the slow photon effect of the multilayer porous structure, which can also increase the probability of the contact between Rhodamine B (RhB) with the active sites of the catalyst. Also, the synergistic effect of the generated TiO₂/ZrTiO₄ heterojunction and built-in oxygen vacancy defects jointly promoted the separation of photogenerated carriers. Thus excellent adsorption rate (75.6%, 60 min) and photodegradation rate (95%, 90 min) of the catalyst were obtained. Furthermore, the up-shifted conduction band and valence band maximum positions are beneficial for the mobility of photogenerated holes and inhibit their reaction with H₂O to generate ·OH, while the photogenerated electrons can react with O₂ to form ·O₂⁻, resulting that the holes and ·O₂⁻ participated in the photodegradation of RhB over the as-prepared catalyst.     

Preparation of SiO2–SiC composites with a precursor method

SiO₂–SiC composite particles were prepared through a hybrid sol–gel precursor process. Compacts were prepared by using a conventional sintering process. The techniques of DSC–TG, SEM and XRD were use to characterize the composite particles and the sintered compacts. It was found that a core–shell structure was constructed in the composite particles with cores of SiC and shells of amorphous SiO₂. Nucleation of SiO₂ occurred at about 1200 °C. The optimized sintering temperature for 30SiO₂–70SiC (vol.%) composites was about 1400 °C with a relatively homogeneous microstructure. The maximum density was about 2.03 g cm^?3.     

复合氧化物TiO2/SiO2性质研究

The nanometer particles of TiO2 and TiO2/SiO2 oxides were prepared by sol-gel and supercritical fluid drying method. The properties of TiO2 and TiO2/SiO2 were characterized by means of BET(Brunner-EmmettTeller method), TEM(transmission electron microscopy), SEM(scanning electron microscopy), XRD(X-ray diffraction) and FTIR(Fourier transform-infrared) techniques. The effects of different preparation route, prehydrolysis and non-prehydrolysis, on the properties of TiO2/SiO2 oxide were also examined. Experimental results show that the thermal stability of pure TiO2 is improved greatly when it is mixed with SiO2 in nanometer level. The composite TiO2/SiO2 oxides form Ti-O-Si chemical bonds, which creates new BrSnsted acidity sites. The acidity character is related to TiO2/SiO2 chemical composition and preparation methods. The acidity of TiO2/SiO2 oxides by prehydrolysis is greater than that of by non-prehydrolysis. Ti atom is rich on the surface of TiO2/SiO2.     

Phase equilibria studies in the CaO–SiO2–Al2O3–MgO system with CaO/SiO2 ratio of 0.9

Phase equilibria and liquidus temperatures in the CaO–SiO₂–Al₂O₃–MgO system at a CaO/SiO₂ weight ratio of 0.9 in the liquid phase have been experimentally determined employing high-temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Isotherms at 1573, 1623, 1673, and 1773 K were determined and the primary phase fields of wollastonite, melilite, olivine, periclase, spinel, and corundum have been located. Compositions of the olivine and melilite solid solutions were analyzed and discussed. Comparisons between the newly constructed diagram, existing data, and FactSage predicted phase diagrams were performed and differences were discussed. The present study will be useful for guidance of industrial practices and further development of thermodynamic modeling.