Palladium within ionic liquid functionalized mesoporous silica SBA-15 and its catalytic application in room-temperature Suzuki coupling reaction

Initially, pore walls of mesoporous silica SBA-15 with template were modified with chlorotrimethylsilane. Then imidazolium salts were similarly incorporated covalently in the inner pore walls of mesoporous silica SBA-15 albeit without the template. Finally, palladium salts were introduced into the pore channels of the previously processed mesoporous silica via electrostatic interaction. The resulting palladium catalysts demonstrated exceptional activity for the room-temperature Suzuki Coupling reaction in aqueous-organic mixed solvents and good recycling ability for at least 4-6 times.

Nickel complexes catalyzed Heck reaction of iodobenzene and methyl acrylate

Nickel appears the most promising for the replacement of palladium among the inexpensive transition metals for that it is active for Heck reaction and about 500 times cheaper than palladium. In this article, we describe our recent results in the area of nickel-catalyzed Heck vinylations. Main focus is on the influence of ligand concentration in different organic solvents and the effects of the addition of water. The conversion is high in NMP and increases with increasing of PPh3/Ni ratio; in ethanol and toluene the conversion presents a maximum value on Ni(PPh3)(2). The effect of the addition of water is sensitive to the concentration of PPh3 and the nature of solvent, it was well explained with the formation and transfer of the active species in the different solvent systems.

Reaction-controlled phase transfer catalysis for styrene epoxidation to styrene oxide with aqueous hydrogen peroxide

The epoxidation of styrene catalyzed by a reaction-controlled phase transfer catalyst [(C18H37(30%)+C16H33(70%))N(CH3)(3))(3)](3)-[PW4O16] with H2O2 in a biphasic medium was investigated. Under certain conditions, the selectivity for styrene oxide was 95%, the conversion of styrene based on H2O2 was 85%, and the reaction time was less than 1 h. During the reaction, this catalyst powder formed soluble active species by the action of H2O2, was recovered as a precipitate, and was reused after H2O2 was used up. After two times recycling, the catalyst kept almost the same activity.

Numerical Simulation of Gaseous Detonation of H_2-O_2 Mixture with Detailed Chemical Reaction Model

采用高精度的ENO格式和基于基元化学反应的真实化学反应模型求解氢氧混合气体一维爆轰波的精细结构。采用直接起爆方法得到稳定传播的爆轰波,计算的爆轰波阵面参数和实验相当符合。对爆轰波反应区化学反应的研究表明,参与反应的不同组分具有不同类型的变化特征。网格尺寸影响的研究表明,计算结果的精度随着网格尺寸的增加而增加,并能保持较好的收敛性。移动网格研究结果表明,网格运动速度和爆轰速度接近时,两者的相互作用对计算结果产生一定影响。

Forward-Running Detonation Drivers for High-Enthalpy Shock Tunnels

To improve the quality of driving flows generated with detonation-driven shock tunnels operated in the forward-running mode, various detonation drivers with specially designed sections were examined. Four configurations of the specially designed section, three with different converging angles and one with a cavity ring, were simulated by solving the Euler equations implemented with a pseudo kinetic reaction model. From the first three cases, it is observed that the reflection of detonation fronts at the converging wall results in an upstream-traveling shock wave that can increase the flow pressure that has decreased due to expansion waves, which leads to improvement of the driving flow. The configuration with a cavity ring is found to be more promising because the upstream-traveling shock wave appears stronger and the detonation front is less overdriven. Although pressure fluctuations due to shock wave focusing and shock wave reflection are observable in these detonation-drivers, they attenuate very rapidly to an acceptable level as the detonation wave propagates downstream. Based on the numerical observations, a new detonation-driven shock tunnel with a cavity ring is designed and installed for experimental investigation. Experimental results confirm the conclusion drawn from numerical simulations. The generated driving flow in this shock tunnel could maintain uniformity for as long as 4 ms. Feasibility of the proposed detonation driver for high-enthalpy shock tunnels is well demonstrated.

Microscopic theory of chemical-reaction rate

In this paper we deduce the formulae for rate-constant of microreaction with high resolving power of energy from the time-dependent Schrdinger equation for the general case when there is a depression on the reaetional potential surface (when the depression is zero in depth, the case is reduced to that of Eyring). Based on the assumption that Bolzmann distribution is appropriate to the description of reactants, the formula for the constant of macrorate in a form similar to Eyring's is deduced and the expression for the coefficient of transmission is given. When there is no depression on the reactional potential surface and the coefficient of transmission does not seriously depend upon temperature, it is reduced to Eyring's. Thus Eyring's is a special case of the present work.