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Dielectric properties of plasma polymerized PVCa and composite PVCa:Au films had been analyzed in the frequency range from 10 to 105 Hz. In order to explain experimental data obtained the modification of Maxwell-Garnett and Bruggeman self-consistent models for the case of three-component composite has been done. The theoretical analysis performed allows to determine peculiarities of dielectric behavior of a three-component system, as well as to disclose the procedure of evaluation of third-component parameters. Results of this analysis are in agreement with experimental ones. 相似文献
55.
Isabel W. C. E. Arends Roger A. Sheldon Martin Wallau Ulf Schuchardt 《Angewandte Chemie (International ed. in English)》1997,36(11):1144-1163
Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O2, H2O2, and RO2H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted. 相似文献
56.
Nunes CD Valente AA Pillinger M Rocha J Gonçalves IS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4380-4390
Mo K-edge XAFS spectra have been measured for ordered mesoporous silica MCM-41 grafted with the complexes [MoO2X2(thf)2] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt. % Mo are obtained; the Mo K-edge EXAFS results indicate the co-existence of isolated surface-fixed monomeric species [MoO2[(-O)3SiO]2(thf)(n)] and [MoO2[(-O)3SiO]X(thf)(n)]. When Et3N is used in the grafting reactions, materials with 4 wt. % Mo are obtained. The EXAFS data for the material prepared using [MoO2Cl2(thf)2] and Et3N indicate the presence of dinuclear species with two Mo(VI) centres, each with two Mo=O groups and each linked by one or two oxo bridges (Mo...Mo 3.27 A). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four-coordinate dioxomolybdenum(VI) and trioxomolybdenum(VI) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X-ray diffraction, N2 adsorption analysis, MAS NMR (13C, 29Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid-phase oxidation of various olefins and alcohols with tert-butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo-bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing. 相似文献
57.
基于一类异族分布的混合寿命模型, 给出了在一/二组样本下的I/II型截尾试验下的贝叶斯密度估计方法; 给出了实例; 并提出了一些问题和解决方法. 相似文献
58.
佘波 《科技情报开发与经济》2005,15(9):202-204
分析了企业在成本竞争中的约束因素,阐述了同质成本与异质成本的概念及内涵,指出异质成本对总成本的影响弹性一定大于同质成本对总成本的影响弹性。 相似文献
59.
一种基于多分类支持向量机的网络入侵检测方法 总被引:11,自引:0,他引:11
构造了一种基于异构数据距离的径向基核函数,可直接应用于异构的网络数据,并利用实验数据得到修正的基于异构数据距离的径向基核函数(I-HVDM-RBF),从而减少了支持向量的个数,降低了运算量,采用I-HVDM-RBF核函数和一对一方法构造了多分类支持向量机来进行网络入侵检测,检测选用美国国防部高级研究计划局入侵检测评测数据,结果表明:与Ambwani方法比较,其检测精度提高了约3%,支持向量个数减少了268个,检测时间缩短了5min;与Lee方法比较,其拒绝服务攻击、远程到本地攻击和普通用户到超级用户攻击的检测精度分别高出73%、19%和3%。 相似文献
60.
介绍了新型太阳能聚光器的设计原理,分析了设计中的三个问题,提出了最佳设计值,探讨了制造过程中的工艺问题。 相似文献