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11.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
12.
陈海珍 《宁波大学学报(理工版)》2004,17(4):444-448
选用了钛酸丁酯、硬脂酸和乙二醇作为表面活性剂,采用表面化学修饰和表面物理修饰2种方法修饰纳米氧化钛,然后分散在乙二醇溶剂中形成溶胶溶液.并通过红外光谱仪、紫外分光计、原子力显微镜,分析了表面化学修饰后的纳米氧化钛表面化学结构的变化,观测了纳米氧化钛溶胶在乙二醇溶剂中稳定性.试验结果表明表面活性剂与纳米氧化钛的表面的不饱和键之间形成了新的化学结构,粒子表面可能接枝上有机长链,提高了纳米粒子在溶剂中的相容性.表面化学修饰后的纳米氧化钛与乙二醇溶剂形成了较稳定的溶胶体系,而且纳米溶胶粒径较小.表面活性剂添加量与纳米粒子添加量控制在(1~1.2):1时,可以获得纳米溶胶粒径较小,同时溶胶稳定性较好的纳米氧化钛-乙二醇溶胶体系. 相似文献
13.
V. I. Sakharov 《Fluid Dynamics》2007,42(6):1007-1016
The results of numerical simulation are presented for thermally and chemically nonequilibrium air plasma flows in a plasmatron discharge channel and underexpanded dissociated and partially ionized air jets flowing past a cylindrical model with a blunt leading edge and cooled copper surface under the experimental conditions realized in a VGU-4 100 kW induction plasmatron (Institute for Problems in Mechanics of the Russian Academy of Sciences) (see, for example, [1, 2]). The nonequilibrium excitation of the vibrational degrees of freedom of the molecules in the modal approximation and the difference between the electron and translational heavy-particle temperatures are taken into account in the calculations. The calculated data on the heat transfer and pressure at the stagnation point are compared with the results obtained within the framework of the thermally equilibrium model. Comparison with the experimental data obtained in the Institute for Problem in Mechanics of the Russian Academy of Sciences (Laboratory for interaction between plasma and radiation and materials) and kindly provided for comparison purposes gives satisfactory agreement. 相似文献
14.
《Fiber and Integrated Optics》2007,26(6):335-342
A fiber-optic chemical sensor (FOCS) for detection of nitrogen dioxide (NO2) molecules is reported. The FOCS presents an optropode structure because of the transmission properties of the sensitive material. The NO2 FOCS is activated by using the semiconductor polymer: regioregular head-to-tail poly(3-octylthiophene-2,5-diyl). The operation wavelength of the sensor is 543.5 nm such that a simple LED and detector can be used for the design of this device. The sensor response decreases after each exposure, demonstrating the reduction in sensitivity as well as irreversibility lower than 5%. However, its properties such as rapid response, high selectivity, high sensitivity (0.43 ± 0.01 muW/ppm), hygroscopic properties, and its operation at room temperature make this kind of FOCS a good alternative for NO2 toxic gas detection. 相似文献
15.
The cocrystal of 1,2-bis(diphenylphosphinoyl)ethane (DPPEO) with phenol (1:1) were studied theoretically with AM1, PM3, MNDO and MINDO/3 semi-empirical methods to elucidate its structure. The bond lengths and angles from theoretical studies of molecule DPPEO/phenol (1:1) were found to be as expected. Theoretical results, concerning with intermolecular van der Waals forces in cocrystal, were compared with the previously obtained experimental data and AM1 results were found to be the best fit for bond lengths and angles of DPPEO/phenol. 相似文献
16.
从现有的PCDFs分子的正辛醇 /水分配系数 (logKow)实验数据出发 ,建立定量结构 性质关系方程(QSPR) .采用G98W程序包中的PM3方法对 13 5个多氯代二苯并呋喃 (PCDFs)分子和二苯并呋喃进行了优化计算 ,作业命令为 #pPM3optfreqscf(conver =9) ,以计算所得的分子轨道能量、碳原子电荷作为PCDFs分子结构描述符 ,运用多元线性回归技术建立了PCDFs的logKow与分子结构描述符的四元方程 ,最优相关系数为 0 .95 0 7,标准偏差为 0 .173 7,经检验该模型的稳健性好 ,并对未有实验数据的 85个PCDFs的logKow进行预测 相似文献
17.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献
18.
19.
The electronic structure and chemical bonding in a recently synthesized inorganic fullerene-like molecule, [CuCl]20[Cp*FeP5]12[Cu-(CH3CN) +
2Cl−]5 has been studied by a density functional approach. Geometrical optimization of the three basic structural units of the molecule
is performed with Amsterdam Density Functional Program. The results are in agreement with the experiment. Localized MO’s obtained
by Boys-Foster method give a clear picture of the chemical bonding in this molecule. The reason why CuCl can react with Cp*FeP5 in solvent CH3CN to form the fullerene-like molecule is explained in terms of the soft-hard Lewis acid base theory and a new concept of
covalence. 相似文献
20.
WANG Bingwu XU Guangxian & CHEN Zhida State Key Laboratory of Rare Earth Materials Chemistry Applications College of Chemistry Molecular Engineering Peking University Beijing China 《中国科学B辑(英文版)》2004,47(2)
The titled inorganic fullerene-like molecule (hereafter abbreviated as IFM) was recently synthe-sized by Bai et al.[1], which attracts a lot of interests from inorganic and organometallic chemists, and questions are raised for this smart molecule: (ⅰ) Why CuCl can react with Cp*FeP5 in solvent CH3CN to form IFM? (ⅱ) What is the nature of chemical bond-ing? (ⅲ) What is the covalence of Cu in this mole-cule? In this paper we intend to answer these questions in terms of the soft-hard … 相似文献