掺杂元素的Lewis酸强度对掺杂In_2O_3电性质的影响

掺杂元素的Ｌｅｗｉｓ酸强度对掺杂Ｉｎ_２Ｏ_３电性质的影响文世杰Ｇ．Ｃａｍｐｅｔ（ＬａｗｒｅｎｃｅＢｅｒｋｅｌｅｙＬａｂｏｒａｔｏｒｙ，ＢｅｒｋｅｌｅｙＣＡ９４７２０，ＵＳＡ）（ＬａｂｏｒａｔｏｉｒｅｄｅＣｈｅｍｉｅｄｕＳｏｌｉｄｅｄｕＣＮＲＳ，Ｕｎｉ...

Lewis acid assisted ring-closing metathesis of chiral diallylamines: An efficient approach to enantiopure pyrrolidine derivatives

Lewis acid assisted ring-closing olefin metathesis (RCM) of chiral diallylamines, using the second generation RCM ruthenium-based catalyst, leads to enantiopure pyrrolidine derivatives in 79-93% yields under very mild conditions. The scope of the olefin metathesis has been expanded.

Comparison Of Shear Banding In Bmgs Due To Thermal-Softening And Free Volume Creation

This paper reports a comparative study of shear banding in BMGs resulting from thermal softening and free volume creation. Firstly, the effects of thermal softening and free volume creation on shear instability are discussed. It is known that thermal softening governs thermal shear banding, hence it is essentially energy related. However, compound free volume creation is the key factor to the other instability, though void-induced softening seems to be the counterpart of thermal softening. So, the driving force for shear instability owing to free volume creation is very different from the thermally assisted one. In particular, long wave perturbations are always unstable owing to compound free volume creation. Therefore, the shear instability resulting from coupled compound free volume creation and thermal softening may start more like that due to free volume creation. Also, the compound free volume creation implies a specific and intrinsic characteristic growth time of shear instability. Finally, the mature shear band width is governed by the corresponding diffusions (thermal or void diffusion) within the band. As a rough guide, the dimensionless numbers: Thermal softening related number B, Deborah number (denoting the relation of instability growth rate owing to compound free volume and loading time) and Lewis number (denoting the competition of different diffusions) show us their relative importance of thermal softening and free volume creation in shear banding. All these results are of particular significance in understanding the mechanism of shear banding in bulk metallic glasses (BMGs).

大块金属玻璃中由热软化和自由体积产生诱导的剪切带行为比较

比较研究了大块金属玻璃中由热软化和自由体积产生诱导的剪切带行为.首先讨论了大块金属玻璃中剪切失稳的热软化和自由体积产生效应.众所周知,在普通金属材料中,由塑性功转变来的热是其形成热塑剪切带的主要原因,并且是与能量直接相关的.与热软化相比,自由体积产生是金属玻璃发生剪切失稳的另外一种主控因素,由自由体积产生诱导的剪切失稳与由热软化诱导的剪切失稳完全不同,失稳判据中不显含能量.尤其是自由体积产生时的长波扰动总是不稳定的.从而,由自由体积产生和热软化耦合时的剪切失稳更像是由自由体积产生引发的.同时,在金属玻璃中,复合自由体积产生提供了一种特殊和内在的剪切失稳特征生长时间.剪切带的特征宽度由剪切带内相应的扩散过程控制:热扩散和自由体积扩散.作为粗略的估计,用无量纲数B,Deborah数(表示失稳生长率和载荷时间关系)和Lewis数(表示不同扩散竞争)表示了热软化和自由体积产生在剪切带形成过程中的相对重要性.这些结果对于理解大块金属玻璃剪切带形成机理具有非常重要的意义.

湍流研究最近半世纪的一些发展

<正>内容一、绪言(Ⅰ)研究湍流的意义(Ⅱ)国外开展湍流研究的情况二、湍流理论的进展(Ⅰ)先把流体动力学方程组平均的理论(a)1950年以前发展情况简述(1)Reynolds方程和混合长度理论(2)各向同性湍流的统计理论(3)具有剪应力的普通湍流理论(b)最近的剪切湍流的半经验理论(c)最近的湍流统计理论(1)E.Hopf理论(2)R.H.Kraichnan直接相互作用理论(8)Lewis等人的分子运动理论(4)Meecham理论。(5)S.Grossmann重正化群法(8)陈善谟统计动力学重复级串法

Long-Wavelength Emission InAs Quantum Dots Grown on InGaAs Metamorphic Buffers

In this work, InAs quantum dots (QDs) grown on a linear graded InGaAs metamorphic buffer layer by molecular beam epitaxy have been investigated. The growth of the metamorphic buffer layers was carefully optimized, yielding a smooth surface with a minimum root mean square of roughness of less than 0.98 nm as measured by atomic force microscopy (AFM). InAs QDs were then grown on the buffer layers, and their emission wavelength at room-temperature is 1.49 mu m as measured by photoluminescence (PL). The effects of post-growth rapid thermal annealing (RTA) on the optical properties of the InAs QDs were investigated. After the RTA, the PL peak of the QDs was blue-shifted and the full width at half maximum decreased.

Effects of zirconia phase on the synthesis of higher alcohols over zirconia and modified zirconia

The catalytic performances of ZrO2-based catalysts were evaluated for the synthesis of higher alcohols from synthesis gas. The crystal phase structures were characterized by X-ray diffraction (XRD) and UV Raman. The results indicated that ZrO2 and Pd modified ZrO2 catalysts were effective catalysts in the synthesis of ethanol or isobutanol, and their selectivities basically depended on the crystal phase of ZrO2 surface. The ZrO2 with surface tetragonal crystal phase exhibited a high activity to form ethanol, while the ZrO2 with surface monoclinic crystal phase exhibited a high activity to form isobutanol. Temperature-programmed desorption (TPD) experiment indicated that the high activity of isobutanol formation from synthesis gas over monoclinic zirconia was due probably to the strong Lewis acidity of Zr4+ cations and the strong Lewis basicity of O2- anions of coordinative unsaturated Zr4+-O2- pairs on the surface of monoclinic ZrO2. (C) 2003 Elsevier B.V. All rights reserved.

Structure and acidity of Mo/H-MCM-22 catalysts studied by NMR spectroscopy

A comprehensive study on physical and chemical properties of Mo/MCM-22 bifunctional catalysts has been made by using combined analytic and spectroscopic techniques, such as adsorption, elemental analysis, and Xe-129 and P-31 NMR of adsorbed trialkylphosphine oxide probe molecules. Samples prepared by the impregnation method with Mo loadings ranging from 2-10 wt.% have been examined and the results are compared with that obtained from samples prepared by mechanical mixing using MoO3 or Mo2C as agents. Sample calcination treatment is essential in achieving a well-dispersed metal species in Mo/MCM-22. It was found that, upon initial incorporation, the Mo species tend to inactivate both Bronsted and Lewis sites locate predominantly in the supercages rather than the 10-membered ring channels of MCM-22. However, as the Mo loading exceeds 6 wt.%, the excessive Mo species tend to migrate toward extracrystalline surfaces of the catalyst. A consistent decrease in concentrations of acid sites with increasing Mo loading < 6 wt.% was found, especially for those with higher acid strengths. Upon loading of Mo > 6 wt.%, further decreases in both Bronsted and Lewis acidities were observed. These results provide crucial supports for interpreting the peculiar behaviors previously observed during the conversion of methane to benzene over Mo/MCM-22 catalyst under non-oxidative conditions, in which an optimal performance was achieved with a Mo loading of 6 wt.%. The effects of Mo incorporation on porosity and acidity features of the catalyst are discussed. (C) 2004 Published by Elsevier B.V.

Direct synthesis of Al-SBA-15 mesoporous materials via hydrolysis-controlled approach

Aluminum-substituted mesoporous SBA-15 (Al-SBA-15) materials were directly synthesized by a hydrolysis-controlled approach in which the hydrolysis of the silicon precursor (tetraethyl orthosilicate, TEOS) is accelerated by fluoride or by using tetramethyl orthosilicate (TMOS) as silicon precursor rather than TEOS. These materials were characterized by powder X-ray diffraction (XRD), N-2 sorption isotherms, TEM, Al-27 MAS NMR, IR spectra of pyridine adsorption, and NH3-TPD. It is found that the matched hydrolysis and condensation rates of silicon and aluminum precursors are important factors to achieve highly ordered mesoporous materials. Al-27 MAS NMR spectra of Al-SBA-15 show that all aluminum species were incorporated into the silica framework for the samples prepared with the addition of fluoride. A two-step approach (sol-gel reaction at low pH followed by crystallization at high pH) was also employed for the synthesis of Al-SBA-15. Studies show that the two-step approach could efficiently avoid the leaching of aluminum from the framework of the material. The calcined Al-SBA-15 materials show highly ordered hexagonal mesostructure and have both Bronsted and Lewis acid sites with medium acidity.

Characterization of the acid sites in dealuminated nanosized HZSM-5 zeolite with the probe molecule trimethylphosphine

The acid sites in dealuminated HZSM-5 zeolite with crystal sizes down to the nanoscale were firstly characterized by the probe molecule trimethylphosphine (TMP). As evidenced by the combination of P-31 CP/MAS NMR, Al-27 MAS and H-1 --> Al-27 CP/MAS NMR measurements, the Bronsted acid sites of both microsized and nanosized HZSM-5 could be decreased upon the dealumination of zeolitic framework after hydrothermal treatment. At the same time, the appearance of Lewis acid sites was observed. The dealuminated nanosized HZSM-5 is easier to form Lewis acid sites than microsized HZSM-5, and the type of Lewis acid sites in nanosized HSM-5 is more than one. In addition, the origin of Lewis acid sites is mainly associated with the aluminum at ca. 30 ppm, in the Al-27 MAS NMR spectra, and only a part of which in the dealuminated HZSM-5 zeolite acts as Lewis acid sites. (C) 2002 Elsevier Science B.V. All rights reserved.

Kinetics of acetic acid esterification with 2-ethoxyethanol over an Al-pillared clay catalyst

The Al-pillared clay catalyst obtained by exposing activated clay powder to sulfuric acid and aluminium salts and calcining in air at 373-673 K, was found to be highly active for the title reaction. The results indicated that pillared layer clay of the mixed oxide has been employed as parent catalysts for their definite structure and special properties which can be modified by the substitution of L and B acid sites cations. Solid acid catalyst of Supported aluminium was found to be highly active and selective at the 373-473 K temperature range for heterogeneous esterification. The activity is mainly attributed to the Lewis (and a considerably small number of Bronsted) acid sites whose number and strength increased due to pillaring. The water produced in the esterification can be induced by Al3+, which makes the catalyst surface to form strong B acid. Their acidities are obtained by pH measurement. If only B acid sites are > 70%, and pH < 1 in the 2-ethoxyethanol, there exists an activity of esterification. The used catalyst gave identical results with that of the fresh one. X-ray diffraction spectra show that the composition and active phase of the used catalysts are the same as the fresh ones. The kinetic study of the reaction was carried out by an integral method of analysis. The kinetic equation of surface esterification is y = 2.36x - 0.98.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.