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121.
The decomposition of 1,1‐dimethyl‐1‐silacyclobutane (DMSCB) on a heated tungsten filament has been studied using vacuum ultraviolet laser single photon ionization time‐of‐flight mass spectrometry. It is found that the decomposition of DMSCB on the W filament to form ethene and 1,1‐dimethylsilene is a catalytic process. In addition, two other decomposition channels exist to produce methyl radicals via the Si? CH3 bond cleavage and to form propene (or cyclopropane)/dimethylsilylene. It has been demonstrated that both the formation of ethene and that of propene are stepwise processes initiated by the cleavage of a ring C? C bond and a ring Si? C bond, respectively, to form diradical intermediates, followed by the breaking of the remaining central bonds in the diradicals. The formation of ethene via an initial cleavage of a ring C? C bond is dominant over that of propene via an initial cleavage of a ring Si? C bond. When the collision‐free condition is voided, secondary reactions in the gas‐phase produce various methyl‐substituted 1,3‐disilacyclobutane molecules. The dominant of all is found to be 1,1,3,3‐tetramethyl‐1,3‐disilacyclobutane originated from the dimerization of 1,1‐dimethylsilene. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
122.
Laia Vilà‐Nadal José Pedro Sarasa Dr. Antonio Rodríguez‐Fortea Dr. Joan Igual Dr. Leonid P. Kazansky Dr. Josep M. Poblet Prof. Dr. 《化学:亚洲杂志》2010,5(1):97-104
DFT calculations were carried out to study 183W NMR chemical shifts in the family of the Keggin anions with formula α‐[XW12O40]q? (X=B, Al, Si, P, Ga, Ge, As, Zn), in the β‐ and γ‐[SiW12O40]4? geometric isomers, in the derivative Dawson anion [P2W18O62]6?, and in the most symmetrical Lindqvist [W6O19]2? anion and its derivative [W10O32]4?. In this article, we show that the geometry employed in the calculation of NMR chemical shifts in polyoxotungstates is extremely important if we want to be quantitative. Using very large basis sets of QZ4P quality and taking into account the conductor‐like screening model (COSMO) to account for solvent effects (aqueous and organic solutions), good geometries were found for the polyoxoanions. From these optimal geometries the 183W NMR chemical shifts were computed with the more standard basis sets of TZP quality and including spin–orbit corrections inside the zero‐order regular approximation (ZORA) to describe the relativistic effects of the internal electrons. With this strategy the mean absolute error between experimental and theoretical values was found to be less than 10 ppm, which is similar to the experimental error. We also discuss how the geometry of the polyoxoanion influences on the shielding. 相似文献
123.
以间苯二酚和甲醛为炭源, F127 (EO106PO70EO106) 为结构导向剂, 在酸性水/乙醇溶液中引入 (NH4)6Mo7O24•4H2O 或 (NH4)2WO4 溶液, 经静置自组装形成凝胶, 再于 N2 中焙烧即合成出金属碳化物修饰的有序介孔炭材料. 结果表明, 金属离子的种类和用量对碳化物的分散度和介孔炭的有序度影响很大. 通过控制金属离子的用量可制备出粒径为 3~5 nm 且高度分散在介孔炭骨架中的碳化物粒子. 与分步浸渍法相比, 一步法制备的碳化物具有更高的分散度和催化肼分解活性. 相似文献
124.
125.
以富营养化的太湖梅梁湾为研究对象,利用平面光极、高分辨率平衡式间隙水采样(HR-Peeper)装置和薄膜扩散梯度(DGT)技术获取沉积物水界面溶解氧(DO)二维平面和溶解态/生物有效态钨(W)一维垂向分布信息,分析铜锈环棱螺分解对太湖底泥中钨迁移的影响效应。试验结果表明:铜锈环棱螺死亡分解后会迅速降低沉积物水界面DO浓度,形成厌氧环境,引起间隙水及上覆水中溶解态钨质量浓度的增加,溶解态钨平均质量浓度增加幅度是对照组的28.92%~11446%,显著提升了沉积物水界面钨的生物有效性(DGT所测结果);与钨质量浓度变化类似,铜锈环棱螺分解前期(第8天)沉积物间隙水中铁、锰质量浓度同步增加且与钨浓度变化呈显著正相关(R2≥0.716,p<0.01)关系,水相中溶解态钨质量浓度增加是由厌氧环境下沉积物中铁锰氧化物还原溶解所致,分解后期(第16天和36天)间隙水中钨质量浓度的增加主要是由于铜锈环棱螺体内累积的钨释放所致。 相似文献
126.
In this paper, porous WO3 films were prepared by anodic oxidation of metallic tungsten (W) films deposited on alumina substrates. The structural and morphological properties of the porous WO3 films were investigated using field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). A large number of cracks appeared on the surface of films after anodization, which makes the films porous. The porous WO3 sensors achieved their maximum response values to NO2 at a low operating temperature of 150 °C. The porous WO3 sensors showed high response values, great stability and fast response-recovery characteristics to different concentration of NO2 gas due to the high specific surface area and special structural and morphological properties. 相似文献
127.
128.
利用作者试验室合成的捕收剂采用离子浮选法进行了钨钼分离.对于(NH4)2WO4溶液和Na2WO4溶液体系,每克钼捕收剂用量为676g的条件下,对于含钼量为04~12g/L的料液,其除钼率可达到94%~99%. 相似文献
129.
Paula C. Barbosa Luísa C. Rodrigues Maria Manuela Silva Michael J. Smith Prudência B. Valente Alexandra Gonçalves Elvira Fortunato 《先进技术聚合物》2011,22(12):1753-1759
Solid polymer electrolyte (SPE) systems based on interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices, with lithium perchlorate as guest salt, were prepared. These electrolytes were presented as free‐standing films, and their thermal and electrochemical properties were characterized by conductivity and electrochemical stability measurements. The properties of the interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices as the electrolyte component of a solid‐state electrochromic device are reported and the results obtained suggest that this electrolyte provides an encouraging performance in this application. The most conducting electrolyte composition of this SPE system is the formulation designated as SPE2‐0PC (5.01 × 10?4 S cm?1 at about 57°C). The lowest decomposition temperature was registered with the SPE6‐15PC composition (233°C). The average transmittance in the visible region of the spectrum was above 41% for all the samples analyzed. After coloration the device assembled with 71 wt% PC presented an average transmittance of 15.71% and an optical density at 550 nm of 0.61. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
130.
Rao A.V. Prasada Paik Dong Soo Komarneni S. 《Journal of Sol-Gel Science and Technology》1997,10(2):221-229
Powders and thin films of barium sodium niobate, Ba4Na2Nb10O30, of filled tungsten bronze type ferroelectric were processed by a sol-gel route using barium metal, niobium ethoxide and sodium methoxide as precursors. Polycrystalline powder resulted after heat treating the gel powder at or above 650°C. Thin films of Ba4Na2Nb10O30 showed no preferred orientation on Si(100), Pt/Si(100) and sapphire substrates. Hysteresis measurements at 1 kHz for the thin films annealed at 750°C, obtained using a prehydrolyzed precursor solution, and gave remanent polarization of 17.34 µC/cm2 and coercive field of 62.5 kV/cm. Microstructural investigation of surface morphology of these films revealed grains about 0.3 µm in size. Prehydrolysis of the precursor solution was found to be necessary to achieve dense films with ferroelectric properties. 相似文献