Kinetics of phenol hydrogenation over supported palladium catalyst

Kinetics of vapor phase hydrogenation of phenol to cyclohexanone over Pd/MgO system has been studied in a flow microreactor under normal atmospheric pressure. The reaction rate is found to be negative order with respect to the partial pressure of phenol and has increased from −0.5 to 0.5 with increasing temperature (473 to 563 K). The apparent activation energy (E_a) of the process is found to be close to 65 kJ per mol. On the basis of kinetic results a surface mechanism is proposed.     

The interfacial conformation of polypropylene glycols and foam behaviour

The foam behaviour of low molecular weight polypropylene glycols (PPG) was investigated as a function of concentration and molecular weight (190–2000 g mol⁻¹). For each polypropylene glycol, foam stability increases with concentration and passes through a maximum, beyond which foamability is suppressed as the solubility limit of the glycol is exceeded and droplets of glycol form. Light-scattering data as well as static and dynamic surface tension results provide the key information leading to these interpretations. A maximum in foamability was observed for the PPG molecules with increasing molecular weight (caused by a change in molecular conformation at the interface). This suppresses the Marangoni effect and leads to a decrease in foam stability.     

Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

荧光光谱法研究蛋白质构象的电磁-温度协同效应

长期以来电磁生物效应受到人们普遍关注，近年来从各个角度进行了相关研究。电磁－温度协同效应是当前的热点。本研究通过电磁场及温度协同对蛋白质影响的研究，发现蛋白质在电磁场作用下的不可逆变性，而且这种变性也遵循Arrhenius规律，并进一步得出电磁－温度协同作用的蛋白质变性模型。本文从分子反应动力学的角度解释了电磁－温度协同效应，并对非热效应作了一定的探讨。     

Methane activation on Ni(1 1 1): Effects of poisons and step defects

We have, theoretically and experimentally, investigated the dissociation of methane on the terraces and steps of a Ni(1 1 1) surface. Using Density Functional Theory (DFT) total energy calculations combined with Ultra High Vacuum (UHV) experiments, we find that the steps exhibit a higher activity than the terraces. We have, furthermore, investigated how carbon and sulfur present on the surface will deactivate the steps, leaving only the terraces active. We find the intrinsic sticking probabilities of methane on the steps and terraces at 500 K to be 2.8 × 10⁻⁷ for the steps and 2.1 × 10⁻⁹ for the terraces, in complete agreement with our calculated difference in activation energy of 17 kJ/mol.     

Energy levels in doped SiGe quantum well studied by admittance spectroscopy

SiGe/Si quantum wells (QWs) with different Boron doping concentrations were grown by molecular beam epitaxy (MBE) on p-type Si(1 0 0) substrate. The activation energies of the heavily holes in ground states of QWs, which correspond to the energy differences between the heavy hole ground states and Si valence band, were measured by admittance spectroscopy. It is found that the activation energy in a heavily doped QW increases with doping concentration, which can be understood by the band alignment changes due to the doping in the QWs. Also, it is found that the activation energy in a QW with a doping concentration of 2 × 10²⁰ cm⁻³ becomes larger after annealing at a temperature of 685 °C, which is attributed to more Boron atoms activation in the QW by annealing.     

Magnetisation reversal in media with perpendicular anisotropy

In this paper, we discuss two key aspects of magnetisation reversal in magnetic thin films with perpendicular anisotropy. Firstly, a study has been made of the additional field required to erase data written perpendicular to a thin film recording disk as the linear data density is increased. It has been found that an increase in data density from 40 to 360 kfci results in an increase of 1.25 kOe in the field required to erase the data. Secondly, the effect of varying the level of exchange coupling by co-sputtering CoCrPt samples with SiO₂ has been studied using a characterisation technique that is independent of the self-demagnetising field. It has been found that the samples are fully exchange de-coupled when the film contains >9.8% SiO₂ and the activation volume of reversal remains constant for higher levels of SiO₂.     

担载型铂催化剂上甲烷活化的TPSR研究

用程序升温表面反应手段，系统地考察了甲烷在Ｐｔ催化剂上的吸附活化特征及甲烷分解后产生的表面碳物种。结果表明，ＣＨ４确能在ＳｉＯ２担载型Ｐｔ催化剂表面发生解离吸附，生成复杂的碳物种。这些碳物种间可发生相互转化。     

四氯化锆四元催化体系中乙烯齐聚反应的动力学研究

研究了四氧化锆作主催化剂的四元催化体系中，乙烯压力、催化剂浓度和温度对乙烯齐聚反应的影响．测定了稳定态下乙烯齐聚反应的宏观动力学方程和表观活化能．     

Thermoanalytical characterization of carbon/carbon hybrid material, Apple Woodceramics

Woodceramics, a carbon/carbon composite of plant-originated carbon reinforced by glassy carbon from phenolic resin, was prepared from apple pomace at carbonizing temperatures of 1073 K (AWC800) and 1473 K (AWC1200), and characterized by thermoanalytical methods and X-ray diffraction (XRD). Simultaneous differential scanning calorimetry (DSC) and thermogravimetric (TG) showed complicated overlapping reactions similar to those of coal. The initial temperature of pyrolysis was obtained by fitting logistic functions to observed TG data. The results suggested that AWC1200 contained more volatile matter than AWC800. In an inert atmosphere, complicated devolatilization takes place. In an oxidizing atmosphere, thermal change occurs roughly in four steps: desorption of physically adsorbed matter; pyrolysis into aliphatic and aromatic fragments; ignition; combustion of char. The oxidation resistance of AWC1200 was superior to AWC800.