Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

Metalorganic chemical vapor deposition of silver thin films for future interconnects by direct liquid injection system

Deposition of Ag films by direct liquid injection-metal organic chemical vapor deposition (DLI-MOCVD) was chosen because this preparation method allows precise control of precursor flow and prevents early decomposition of the precursor as compared to the bubbler-delivery. Silver(I)-2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionato-triethylphosphine [Ag(fod)(PEt₃)] as the precursor for Ag CVD was studied, which is liquid at 30 °C. Ag films were grown on different substrates of SiO₂/Si and TiN/Si. Argon and nitrogen/hydrogen carrier gas was used in a cold wall reactor at a pressure of 50–500 Pa with deposition temperature ranging between 220 °C and 350 °C. Ag films deposited on a TiN/Si diffusion barrier layer have favorable properties over films deposited on SiO₂/Si substrate. At lower temperature (220 °C), film growth is essentially reaction-limited on SiO₂ substrate. Significant dependence of the surface morphology on the deposition conditions exists in our experiments. According to XPS analysis pure Ag films are deposited by DLI-MOCVD at 250 °C by using argon as carrier gas.     

Mass Transfer in a Flat Gas/Liquid Interface using non‐Newtonian Media

Gas/liquid mass transfer has been investigated using a stirred vessel gas/liquid contactor using non‐Newtonian media and carbon dioxide as absorbent and gas phase, respectively. The volumetric mass transfer coefficients at different operational variables have been determined. Non‐Newtonian media (liquid phase) were prepared as aqueous solutions of sodium carboxymethyl cellulose salt. The influence of the rheological properties, polymer concentration, stirring rate, and gas flow rate on mass transfer was studied for these liquid phases. Kinematic viscosity and density experimental data were used to calculate the average molecular weight corresponding to the polymer employed. The Ostwald model has been used to fit the rheological behavior of aqueous solutions of the polymer employed as absorbent phase. Reasonably good agreement was found between the predictions of the proposed models and the experimental data of mass transfer coefficients.     

Alumina-supported catalysts for propane oxidative dehydrogenation from mixed VXM(6−X)O19 (M=W, Mo) hexametalate precursors

γ-Al₂O₃ supported vanadium oxides were modified by tungsten and molybdenum oxides in order to improve dispersion and selectivity towards olefins in propane oxidative dehydrogenation (ODH). Both vanadium–tungsten and vanadium–molybdenum catalysts were obtained by adsorption of mixed isopolyanions (VW₅O₁₉⁵⁻, V₂W₄O₁₉⁴⁻, VMo₅O₁₉⁵⁻ and V₂Mo₄O₁₉⁴⁻) from aqueous solutions. The isopolyanion solutions were characterized by UV-Vis and ⁵¹V NMR spectroscopy. Vanadium, vanadium–tungsten and vanadium–molybdenum precursors and catalysts were also characterized by UV-Vis (diffuse reflectance) and solid state ⁵¹V NMR spectroscopy. An improved selectivity to propene in the presence of tungsten and molybdenum in VO_x/γ-Al₂O₃ was observed and attributed to dilution of vanadium by tungsten or molybdenum oxides on the γ-Al₂O₃ surface.     

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.     

Anthocyanin composition of the red wine Babić affected by maceration treatment

Identification of anthocyanins in the wine made of the Croatian autochthonous grape variety of Babić (Vitis vinifera L.) was carried out and their profile was determined by means of high-performance liquid chromatography with diode array and mass spectrometric detection. Dependence of anthocyanins content and profile on maceration treatment conditions was investigated. Statistically significant differences of anthocyanins concentration in wines Babić produced by various maceration treatments were confirmed by the use of multivariate analysis of variances. The investigation results indicated that the maceration temperature exerts higher influence on anthocyanins concentration than the duration of maceration. In addition, on the basis of anthocyanin composition and using different multivariate statistical analyses, differentiation of wines Babić according to maceration treatments was procured.     

Dynamics of liquid-filled spacecraft

A method is presented for simulating coupled liquid-solid dynamics. An important example of a coupled liquid-solid system is a satellite carrying fuel. The dynamics of the satellite and the onboard fuel influence each other, which may lead to satellite motion that is uncontrollable. For better understanding of the complex dynamics of coupled systems, a numerical model is developed. The model consists of two parts. The first part that solves the liquid motion is only briefly discussed here. The focus in this paper is on the way in which the dynamics of the liquid and the solid body are coupled. For this, the governing equations are presented in which terms appear that represent the force and torque on the solid body due to the sloshing liquid. The governing equations are rewritten such that the discrete approximation of these equations can be integrated in a stable manner for arbitrary liquid/solid mass ratios. Results are presented demonstrating the stability of the present model. A grid-refinement study and a time-step analysis are performed. Finally, the flat-spin motion of a satellite, partially filled with liquid, that flew in 1992 as part of the Wet Satellite Model experiment is studied. Results from the simulation are compared with the actual flight data.     

Mean residence time of gas in mechanically agitated gas–liquid contactors

In the present study of gas–liquid contactors, mean residence/contact time was calculated from knowledge of superficial velocity and the gas phase hold-up, for various gas rates and impeller geometry and speeds, and compared with values obtained from RTD measurements. A new correlation, involving Flow Number, Froude Number, system geometry and the physical properties, is proposed. This uses the authors data and those available in literature.     

芝麻营养原液的开发与研究

本文对芝麻营养保健成分的提取进行了系统的研究。确定了芝麻营养原液的制取工艺。为充分发挥芝麻的营养保健作用开辟了新的途径。     

超细Fe3O4粒子表面包覆酞菁钴性质研究

本文研究了合成载氧体的金属有机化学液相淀积法制造工艺，所得产物经ＴＥＭ、ＸＰＳ、Ｍｏｓｓ－ｂａｕｅｒ谱和Ｂ－Ｈ仪等手段，研究了它的结构和磁性能。实验表明，酞青钴以薄层形式包覆在Ｆｅ＿３Ｏ＿４的表面，封闭了Ｆｅ＿３Ｏ＿４的表面孔洞，稳定了Ｆｅ＿３Ｏ＿４的物相，增强了磁性能。