固体强酸催化剂Pd/WO3-ZrO2的制备及其对正庚烷异构化反应的催化性能

 采用共沉淀方法制备了固体酸载体WO3-ZrO2,考察了W含量和焙烧温度等对WO3-ZrO2酸性和物相结构的影响,并且考察了Pd/WO3-ZrO2催化剂对正庚烷异构化反应的催化性能. 结果表明,Pd/WO3-ZrO2催化剂的催化性能与固体强酸的W含量及晶相结构密切相关. 在w(W)=13.2%～15.8%时,经700～800 ℃焙烧,WO3在ZrO2表面达到单层分散,且大部分ZrO2以四方晶相存在,所制备的0.5%Pd/WO3-ZrO2对正庚烷异构化反应的催化活性可达到70.4%,选择性可达到81.0%.     

Fabrication of silica nanoparticles and hollow spheres using ionic liquid microemulsion droplets as templates

Silica products with two different morphologies were synthesized using nonaqueous ionic liquid microemulsion droplets as templates. The morphologies of the obtained products were characterized by both transmission electron microscopy (TEM) and scanning electron microscopy (SEM). By adjusting the reaction conditions, ellipsoidal nanoparticles were formed under acidic conditions, while hollow silica spheres were obtained under alkaline conditions. It is demonstrated that the size distribution of hollow silica spheres was narrower than that of the ellipsoidal nanoparticles. The various vibration modes of different functional groups in the silica materials were revealed by Fourier transform infrared (FTIR) spectroscopy. The two samples were both shown to be amorphous, not crystalline by X-ray diffraction (XRD). A simple diagram of the formation process including the hydrolysis and condensation reactions is given. Furthermore, a probable mechanism for the formation of silica materials under acidic or alkaline conditions is presented, which may be helpful for better understanding the different silica materials obtained under different conditions.     

Finite-time convergent guidance law with impact angle constraint based on sliding-mode control

In this paper, a finite-time convergent sliding-mode guidance law with terminal impact angle constraint is presented. The guidance law insures that the line-of-sight angular rate will converge to zero before the final time of the guidance process. Meanwhile the flight-path angle will meet the terminal impact angle requirement. Based on the finite-time convergence stability theory and the variable structure control theory, the finite convergence time is determined. Finally, the simulation results show that the guidance law is effective.     

基于壁面主动变形的湍流减阻控制研究

采用谱方法, 对反向控制下壁面主动变形的槽道湍流进行了直接数值模 拟研究. 结果表明, 在壁面最大变形量小于5倍黏性尺度条件下, 压差阻力可略, 摩擦阻力 降低7.6%. 施加控制后, 湍流强度和雷诺应力受到明显抑制, 平均速度剖面对数区上移. 受壁面法向运动的影响, 条带结构强度减弱、尺度变大; 流向涡外移且强度减弱, 其倾斜和 抬起的角度均有不同程度的减小. 壁面变形呈现流向拉长的凹槽结构, 其平均间距 为90倍黏性尺度.     

In situ AFM investigation of 2D nucleation on the (100) face of KDP

Surface morphology of the (100) face of potassium dihydrogen phosphate (KDP) crystals which were grown at different supersaturations at 25 °C was investigated by in situ atomic force microscopy (AFM). Various AFM images of 2D nucleation under different growth conditions were presented. It is found that the growth of KDP is controlled by polynuclear nucleation mechanism at the high supersaturation. With reduction of the supersaturation, the growth velocity of 2D nuclei becomes very slow and shows typical anisotropy. It is found that the process of coalescence of 2D nuclei does not lead to defect. The experiments show that the growth mechanism for KDP at 25 °C changes between step flow and 2D nucleation in the supersaturation range of 4.5‐5%. The triangular nuclei which are close to equilateral triangle are observed in the experiment at the supersaturation σ = 6% for the first time, showing typical anisotropic growth. Through observing the dissolution of 2D nuclei, the dissolving process can be regarded as the reverse process of growth. We also find that the microcrystals landing on the surface at σ = 9% would grow and coalesce with each other and there is no observable defect in the coalescence. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

基于液氮低温冷刀系统的冻结组织温度场分布研究

设计了基于液氮的低温冷冻治疗系统,并进行动物组织实验研究,得到组织关键测温点的温度变化;并对冷冻过程进行数值模拟,将实验结果与模拟冷冻结果进行对比,根据二者的差异对数值模拟中采用的组织热物性参数进行修正,使模拟结果更接近于实际冷冻过程.     

Computational mechanistic study of the hydrogenation of carbonate to methanol catalyzed by the Ru(II)PNN complex

Density functional theory computations have been carried out to study the mechanism of hydrogenation-based transformation of dimethyl carbonate to methanol, catalyzed by Ru(II)PNN catalyst. The energetic results show that the catalytic transformation includes three sequential stages consistently involving the catalyst: (stage I) transformation of dimethyl carbonate (3) to methyl formate (5) and methanol; (stage II) transformation of methyl formate 5 to formaldehyde and methanol; (stage III) hydrogenation of formaldehyde to methanol. Stages I and II proceed similarly and follow three steps: hydrogen activation, formation of a hemiacetal intermediate via stepwise hydrogen transfer to dimethyl carbonate in stage I or methyl fomate in stage II, and subsequent decomposition of the hemiacetal intermediate to afford methanol. Hydrogenation via carbonyl insertion into the Ru-H bond is less favorable than the stepwise hydrogen-transfer mechanism. Decomposition of hemiacetal takes places by first breaking the hemiacetal O-H bond to give an alkoxide complex, followed by deprotonation of the benzylic arm ligand to the adjacent methoxy group. Comparing the hydrogenation steps in the three stages, hydrogenation in stage I is most difficult, that in stage II is less difficult, and that in stage III is easiest in terms of both kinetics and thermodynamics. This can be ascribed to the stronger electrophilicity of the carbonyl group in methyl formate or formaldehyde than that in dimethyl carbonate and fewer steric effects between the catalyst and methyl formate or formaldehyde than that between the catalyst and dimethyl carbonate. Thermodynamically, both stages I and II are uphill, but stage III is downhill significantly, which is the driving force for the catalytic transformation. The study indicates that the methanol product could facilitate the hydrogen activation involved in the transformation, implying that transformation could be accelerated by initially adding methanol.     

你真的会玩翻身陀螺吗?

推导翻身陀螺在翻身过程中的角速度,解释为什么不怕速度太快而翻过头、翻身陀螺进动与自转方向"相反",以及并不是自转越快越易翻身.     

油酸钠改性无水硫酸钙晶须及其机理研究

采用油酸钠改性无水硫酸钙晶须(AW),既可以增强无水硫酸钙晶须的疏水性,又可以在晶须表面引入-C=C-增加其功能性。利用晶须在甲基丙烯酸甲酯(MMA)的分散性能探究油酸钠加量、时间、改性温度等因素对改性效果的影响;采用XRD、XPS和DRIFTS探索晶须的吸附及改性机理、Washburn法测定晶须的疏水性能。结果表明随油酸钠用量的增加,分散性能先变好后变差,油酸钠与晶须质量比为1∶100时,沉降高度和沉降速度由油酸钠与晶须质量比为1∶200时的3.1 cm和0.31 cm/min大幅增加到10.6 cm和1.06 cm/min;分散性能开始出现突变时的油酸钠用量随温度升高而增加;DRIFTS表明油酸钠中的油酸根离子主要以物理吸附和化学吸附的方式与钙离子结合存在于晶须表面,其特征吸收峰分别是1 577 cm^-1和1 540 cm^-1的双峰和1 547 cm^-1的单峰;改性后的晶须疏水性较改性前大幅增加,与水的接触角从改性前的0.04°增加到改性后的77.35°。     

Deposition features of Ni on self-assembled microtubule template from biolipid by electroless method

The self-assembly of lipid molecules is in close relationship with the structure and function of a cell membrane. A cell membrane has a variety of lipid molecules. Lipid molecules have their amphiphile na-tures, and their self-assembly can form a variety of thermodynamically stable microstructures, such as single-bilayer or multi-bilayer spherical and ellipsoidal liposome, microcylindrical and microtubular struc-tures[1]. These microstructures exhibit different bio-logical functions in living …