Highly Enhanced Catalytic Stability of Copper by the Synergistic Effect of Porous Hierarchy and Alloying for Selective Hydrogenation Reaction

Supported copper has a great potential for replacing the commercial palladium-based catalysts in the field of selective alkynes/alkadienes hydrogenation due to its excellent alkene selectivity and relatively high activity. However, fatally, it has a low catalytic stability owing to the rapid oligomerization of alkenes on the copper surface. In this study, 2.5 wt% Cu catalysts with various Cu:Zn ratios and supported on hierarchically porous alumina (HA) were designed and synthesized by deposition–precipitation with urea. Macropores (with diameters of 1 μm) and mesopores (with diameters of 3.5 nm) were introduced by the hydrolysis of metal alkoxides. After in situ activation at 350 °C, the catalytic stability of Cu was highly enhanced, with a limited effect on the catalytic activity and alkene selectivity. The time needed for losing 10% butadiene conversion for Cu1Zn3/HA was ~40 h, which is 20 times higher than that found for Cu/HA (~2 h), and 160 times higher than that found for Cu/bulky alumina (0.25 h). It was found that this type of enhancement in catalytic stability was mainly due to the rapid mass transportation in hierarchically porous structure (i.e., four times higher than that in bulky commercial alumina) and the well-dispersed copper active site modified by Zn, with identification by STEM–HAADF coupled with EDX. This study offers a universal way to optimize the catalytic stability of selective hydrogenation reactions.

PREPARATION AND CHARACTERIZATION OF POROUS ALUMINA-TITANIA AEROGEL VIA CO2 SUPERCRITICAL EXTRACTION

Porous aerogel of titania-alumina were prepared by hydrolysis of metal alkoxides and supercritical extraction of the solvent. Monolithic wet-gel of 0.2TiO2-0.8Al2O3, prepared by hydrolysis of metal alkoxides in alcoholic solutions, and the solvent in wet gel was supercritically extracted in CO2 at 60oC and 24Mpa for 2h. Thermal evolutions of the microstructure of the gel were evaluated by differential thermal analysis (TG-DTA), N2 adsorption, scanning electron microscopy and X-ray diffractometer. After calcination at 500oC, the specific surface area of the gel was more than 400m2g-1. The average pore radius of aerogel, about 8nm, was about 50% of that for alumina aerogel, but about 4 times larger than that of the xerogel. The specific surface area of the aerogel was more than 200m2g-1 after calcination at 800oC. The pore size and pore volume of aerogel hardly decreased after calcinations at 800oC, although those values of the xerogel remarkably decreased after calcination up to 800oC. The thermal stability of the microstructure of porous titania-alumina is improved by supercritical extraction. Keywords: Oxides, Sol-gel chemistry, X-ray diffraction, Infrared pectroscopy

XRD Study of the Influence of Heat Treatment on the Microstructure of Sol-Gel Processed ZrO2-Y2O3 Ceramics

ABSTRACTYSZ samples containing 5 and 10 mol% of Y203 were prepared by controlled hydrolysis of metal alkoxides. The dried powders were calcined at 800°C and then they were uniaxially pressed and sintered at different temperatures and next heated at 1400°C (∼ 5 MPa) or annealed at 1600°C for 24 h. The quantitative analysis of the experimental X-ray diffraction (XRD) spectra was performed by Whole Pattern Fitting (WPF). A Pseudo-Voigt (Thompson-Cox-Hastings) was used as shape profile function. The respective phase fractions (wt %) were fitted for both solid state solutions using the scale factor. The heat treatment induced changes are discussed.

Preparation of Sol-Gel Coatings by Electrophoretic Deposition

ABSTRACTThin films of ZrO2 and lead zirconate-titanate, PZT, about 100 to 1000 nm in thickness, were prepared by electrophoretic deposition from transparent sols obtained by hydrolysis of metal alkoxides. Stainless steel plates and Pt-coated glass plates were used as substrates/electrodes. The applied field was up to 20 V/cm. The refractive indices of as dried films were higher than those of dip-coated films. High temperature oxidation of stainless steel plates was suppressed by the ZrO2 coatings. Uniformity of the chemical composition of the as-dried PZT films, determined by Auger electron spectroscopy, was better than the dip-coated PZT films.

Electrical properties of silica-alumina ceramics in nitrogen atmosphere

The SiO2–Al2O3 powders with compositions of 46.5 to 76.6 wt. % Al2O3, synthesized by the hydrolysis of metal alkoxides, were sintered at 1700 °C for 3 h in a reduced pressure of 40 Pa. After sintering, the samples were annealed at 1300 °C for 10 h in air. The densities of sintered samples were higher than 97.0% T.D. The electrical conductivities of the SiO2–Al2O3 ceramics in N2 atmosphere (>99.99%) were measured in the temperature range of 500° to 800 °C by using ac bridge circuit at 120 Hz to 1 MHz and dc circuit at 1 V. The electrical conductivities at 800 °C were 3.4 × 10−7 to 4.3 × 10−6 S cm−1, and decreased with increasing Al2O3 content. The SiO2–Al2O3 ceramics were mixed conductors of oxygen ions and electrons in nitrogen atmosphere. The activation energies of ionic and electronic conductivities were 102 to 143 kJ/mole and 102 to 123 kJ/mole, respectively.