Solvent free liquid phase oxidation of benzyl alcohol using Au supported catalysts prepared using a sol immobilization technique

Solvent free oxidation of benzyl alcohol was investigated in the absence of a base using Au catalysts prepared by sol immobilization on titania and carbon supports. Comparison between the Au supported catalysts revealed that activity and distribution of products was dependent on the nature of support and heat treatment. Specifically, heat pre-treatment of the Au catalysts has a beneficial effect in terms of activity, but is detrimental in terms of selectivity to the benzaldehyde. We conclude that sol immobilization is a suitable technique for preparing gold catalysts with small particle size and narrow particle size distributions and very high activity and selectivity for benzyl alcohol oxidation.     

Synthesis and properties of an alkoxysilane dye containing three electronic donor groups for nonlinear optical applications

In order to obtain an efficient hybrid inorganic–organic nonlinear optical (NLO) materials, an azo-dye containing three electronic donor groups 2,5-dimethyl-4-(4′-nitrophenylazo)phenol (DMNPAP) was synthesized and reacted with 3-isocyanatopropyl triethoxysilane (ICTES) to give an alkoxysilane dye (ICTES–DMNPAP). Molecular structural characterizations for DMNPAP and ICTES–DMNPAP were investigated by elemental analysis, ¹H NMR, FTIR, UV–visible spectra and differential scanning calorimetry (DSC). The alkoxysilane dye could be hydrolyzed and polymerized in the presence of water, and then transparent hybrid films could be fabricated by spin coating on the indium–tin-oxide (ITO) glass substrates. Compared with the dye 4-nitro-4′-hydroxy-azobenzene (NHA) containing only one hydroxyl as donor group, DMNPAP exhibited larger β_CTμ_g value measured by solvatochromic method, and second harmonic generation (SHG) measurement of the hybrid films was in agreement with the result.     

Intercalation of methylene blue in n-alkanethiolated self-assembled monolayers: Versatile electrochemical platforms for characterizing surfactant adsorption on hydrophobic surfaces

A versatile electrochemical platform for characterizing the adsorption of neutral and positively charged surfactants on hydrophobic surfaces was established using methylene blue (MB) as the probe. As a rigid, planar and electroactive species, MB can intercalate inside the regular self-assembled monolayers (SAMs) of n-hexanethiol and exhibit well-defined electrochemical responses. The adsorption of surfactants on the hydrophobic SAMs through the intercalation interaction between the hydrophobic tails of surfactants and the SAMs might change the density of the SAMs and influence the electrochemical behaviors of MB, providing a simple but effective approach for characterizing surfactant adsorption on hydrophobic surfaces. As an example, the adsorptive behaviors of cetyltrimethylammonium bromide (CTAB), a positively charged surfactant, and Triton X-100, a neutral surfactant, on hydrophobic surfaces were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The results showed that these surfactants generally experienced three different adsorptive behaviors: the monomer adsorption at low concentrations, the loose monolayer adsorption at intermediate concentrations and the dense monolayer adsorption at high concentrations. In the case of CTAB, a new additional submonolayer adsorptive behavior between the monomer and the loose monolayer adsorption was observed for the first time, due to its rather long hydrophobic tail.     

Manganese ferrite nanoparticles synthesized through a nanocasting route as a highly active Fenton catalyst

Spinel ferrite MnFe₂O₄ nanoparticles were synthesized by means of a nanocasting technique using a low-cost mesoporous silica gel as a hard template. The magnetic nanoparticles, of <10 nm diameter and with a surface area of around 100 m²/g, were tested as a heterogeneous Fenton catalyst for the decomposition of hydrogen peroxide under neutral and basic conditions. This catalyst shows a much higher activity than previous heterogeneous catalysts reported in the literature, which is mainly ascribed to its small particle size. Furthermore, the magnetic catalyst can be easily separated from the reaction medium by means of an external magnetic field. The effects of residual silica and the purity of the catalyst (hematite formation) on catalytic activity have been studied and correlated. The results obtained show this catalyst to be a suitable candidate for the removal of pollutants in wastewaters by means of the Fenton heterogeneous reaction.     

Preparation of Mesoporous Ni–alumina Catalyst by One-step Sol–gel Method: Control of Textural Properties and Catalytic Application to the Hydrodechlorination of o-dichlorobenzene

Mesoporous Ni–alumina catalysts (Ni–alumina-pre and Ni–alumina-post) were synthesized by one-step sol–gel method using micelle complex comprising lauric acid and nickel ion as a template with metal source and using aluminum sec-butoxide as an aluminum source. The Ni–alumina catalysts showed relatively high surface areas (303 m²/g for Ni–alumina-pre and 331 m²/g for Ni–alumina-post) and narrow pore size distributions centered at ca. 4 nm. Highly dispersed Ni particles were observed in the Ni–alumina catalysts (ca. 5.2 nm for Ni–alumina-pre and ca. 6.8 nm for Ni–alumina-post) after reduction at 550 °C, while a catalyst prepared without a template (NiAl-comp) exhibited inferior porosity with large metal particles (ca. 12.3 nm). Mesoporous Ni–alumina catalysts with different porosity were obtained by employing different hydrolysis step of aluminum source. When aluminum source was hydrolyzed under the presence of micelle complex, a supported Ni catalyst with highly developed framework mesoporosity was obtained (Ni–alumina-post). On the other hand, when aluminum source was pre-hydrolyzed followed by mixing with micelle solution, the resulting catalyst (Ni–alumina-pre) retained high portion of textural porosity. It was revealed that the hydrolysis method employed in this research affected not only textural properties but also metal-support interaction in the Ni–alumina catalysts. It was also found that the Ni–alumina-pre catalyst exhibited weaker interaction between nickel and alumina than the Ni–alumina-post, leading to higher degree of reduction in the Ni–alumina-pre catalyst. In the hydrodechlorination of o-dichlorobenzene, the Ni–alumina catalysts exhibited better catalytic performance than the NiAl-comp catalyst, which was attributed to higher metal dispersion in the Ni–alumina catalysts. In particular, the Ni–alumina-pre catalyst showing 1.5 times higher degree of reduction and larger amounts of o-dichlorobenzene adsorption exhibited better catalytic performance than the Ni–alumina-post catalyst.     

Optimization of the sputter-deposited platinum cathode for a direct methanol fuel cell

The electrodes prepared by a sputtering method were evaluated as the cathodes for direct methanol fuel cells (DMFCs). Pt loading below 0.25 mg cm⁻² achieved higher mass activities than that of 0.5 mg cm⁻² prepared by the paste method, which was general conventional method. However, an increase in Pt loading reduced the catalyst activity for the oxygen reduction reaction (ORR). This result may suggest an increase in only electrochemically inactive Pt. Pt utilization efficiency can be found about ten times higher at Pt loading of 0.04 mg cm⁻². Moreover, addition of Nafion to sputter-deposited Pt cathodes is found possible to improve the catalyst activity for the ORR, but the excess Nafion over the optimum condition reduces the active sites.     

Transformations of sulphur compounds in high-sulphur coals during reduction in the potassium/liquid ammonia system

The two types of high-sulphur coals Mequinenza and Illinois No. 6, in the initial form and subjected to potassium/liquid ammonia reduction, were analysed by atmospheric pressure-temperature programmed reduction (AP-TPR) method. It has been shown that preliminary demineralisation was beneficial for AP-TPR measurements because of the removal of calcium compounds. The reduction of sulphides and disulphides in the potassium/liquid ammonia system was found to lead to formation of aromatic and aliphatic thiols. The presence of the latter is better manifested in the AP-TPR kinetograms when the measurements are performed in the presence of a special reducing mixture. It has been shown that the coal reduction in the potassium/liquid ammonia system apart from transformations of non-thiophene sulphur groups also leads to breaking up of the C-S bonds in some thiophene systems.     

Numerical analysis on reaction injection molding of polyurethane foam by using a finite volume method

Foam reaction injection molding (FRIM) is one of the most popular and useful processes for producing polyurethane foam with a complex geometry. A theoretical model which includes chemical reactions, foaming, and mold filling was developed to analyze FRIM. Energy balance equation was derived by considering polyurethane reaction, water-isocyanate reaction, and evaporation of physical blowing agents. Density and viscosity model was proposed for the bubble suspension, which was assumed to be a homogeneous phase. Based on the theoretical model, three-dimensional numerical simulation for mold filling of the polyurethane foam was carried out to predict flow field, flow front advancement, and density distribution during mold filling. Mold filling of a refrigerator cavity was investigated numerically. The density and thermal conductivity of the foam in the flow front was higher than those in the initially filled region.     

Numerical analysis of particle mixing in a rotating fluidized bed

This paper describes the numerical analysis of particle mixing in a rotating fluidized bed (RFB). A two-dimensional discrete element method (DEM) and computational fluid dynamics (CFD) coupling model were proposed to analyze the radial particle mixing in the RFB. Spherical polyethylene particles (Geldart group B particles) were used as model particles under the assumptions that they were cohesionless and mono-disperse with their diameter of 0.5 mm.The validity of the proposed model was confirmed by the comparison between the calculated degree of particle mixing and the experimental one, which was obtained by measuring the lightness of the recorded image taken by a high-speed video camera. Effects of the operating parameters (gas velocity, centrifugal acceleration, particle bed height, and vessel radius) on the radial particle mixing rate were numerically analyzed. The radial particle mixing rate was found to be strongly affected by the bubble characteristics, especially by the bubble size. The mathematical model for the rate coefficient of particle mixing as functions of operating parameters was empirically proposed. The radial particle mixing rate in a RFB could be well correlated by the three dimensionless numbers: dimensionless acceleration (Ac), bubble Froude number (Fr_b), and dimensionless radius on the surface of particle bed (β_s).     

气体压强对非晶InGaAs薄膜光学常数的影响

论述一种用透射谱包络线法计算非晶薄膜的折射率、消光系数和光学带隙的方法。通过正交实验确定除压强之外的工艺参数,研究压强的改变对薄膜主要光学常数的影响,运用最小二乘法、内插值法在matlab编程基础上,拟合出光学常数曲线,借由观察曲线的特点,分析在低工作气压下,气压的改变对光学常数的影响。