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51.
有机磷配位铐或钴联基配合物是生产难或醇的工业催化剂,一般公认金属氢化物是反应的催化活性物种.通常反应活性物种仅存在干反应状态下,其结构表征非常困难,在许多研究中只能关联催化剂母体与其活性的关系[‘1;而未能揭示出催化的本质,给催化剂设计造成很大困难,因而对催化剂活性物种的直接表征受到普遍关注.B。wn问、Morrista]及本文作者研究组*均采用加压原位红外光谱方法,在烯烃氢甲酸化反应条件下捕捉到HCO(CO)3L存在的信息·但用相同方法在反应条件下,在RhH键特征吸收谱带195O-2200Cm‘内未观测到错氢化物的Rh-… 相似文献
52.
P. Niedzielski M. Siepak B. Dudzińska-Huczuk 《Central European Journal of Chemistry》2003,1(3):314-324
This paper reports the results of an optimisation study for a procedure to determine the total selenium and its inorganic
species, Se(IV) and Se(VI) using atomic absorption spectrometry combined with hydride generation and in-situ trapping of the
analyte on the inner walls of the graphite tube. With the use of the proposed modification, a detection limit (3σ) of 0.018
ng/ml is achieved. This paper presents exemplary results, according to the proposed procedure, for selenium determination
in samples of marine water. The concentrations of selenium in the samples ranged from <0.02 ng/ml to 0.16ng/ml of Se(IV) and
from <0.02 ng/ml to 0.10 ng/ml of Se(VI). 相似文献
53.
以聚丙烯微孔膜为基材,通过扩散控制原位共聚合的方法在人填充了组成沿膜的厚度方向逐渐改变的无规共聚物,X-光电子能谱(XPS)、全反射红外光谱(ATR)以及动态粘弹谱的分析结果。说明所制备得到的合膜具有明显的渐变聚合物性质。 相似文献
54.
M. V. Kirov 《Journal of Structural Chemistry》2003,44(3):420-428
A nanostructural approach to analysis of proton ordering in gas hydrate cages has been worked out within the framework of the topological model of strong and weak H-bonds. The approach involves rejection of the periodic boundary conditions, decomposition of the H-bond net into spherical layers, and two-dimensional drawing of the structure of spherical (spheroidal) fragments in the form of conjugate Schlegel diagrams. To analyze proton ordering in the spherical fragments composed of gas hydrate voids, we used the simulated annealing procedure and the correlation extension method proposed earlier. 相似文献
55.
Phase transition of water restrained by curdlan suspension
annealed at a temperature from 20 to 110°C was investigated by differential
scanning calorimetry (DSC). The melting temperature of water restrained by
annealed curdlan discontinuously decreased at around 60°C, while the amount
of bound water calculated from enthalpy of melting increased at 60°C,
regardless of water content. Using a highly sensitive DSC, curdlan suspension
with various concentrations was studied. It was found that an endothermic
transition was observed at ca. 58°C in a wide range of concentrations.
The transition observed at 60°C is thermo-reversible and both temperature
and transition enthalpy are constant even after gel formation. Well equilibrated
suspension at a temperature lower than 60°C formed no gel. 相似文献
56.
A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization. 相似文献
57.
58.
L. G. Lin Y. Wang J. W. Yan Y. Z. Yuan J. Xiang B. W. Mao 《Electrochemistry communications》2003,5(12):995-999
We report an in situ STM study of a potential-dependent long-range surface restructuring of Au(1 1 1) electrode in neat 1-butyl-3-methylimidazolium tetrafluoroborates (BMIBF4) ionic liquid. Au(1 1 1) undergoes a significant long-range surface restructuring upon cathodic excursion to −1.0 V vs. Pt quasi-reference. The restructuring involves the formation of tiny pits, which then develops into a stable worm-like network with an average width of the network grids 2 nm. Electrochemical annealing occurs at the cathodic limit with the presence of a reduction product of cation BMI+. A smooth surface is recovered with the appearance of the typical (√3 × 22) reconstruction of Au(1 1 1). The surface restructuring is reestablished upon anodic excursion to −1.3 V after the adsorbed reduction product is oxidized. The long-range surface restructuring phenomenon is tentatively explained as a result of partial charge transfer to the weakly adsorbed BMI+, which reduces the metal–metal cohesive energy. In addition, the synergetic effect of the counter anion BF4− may also be involved. The results provide a knowledge of Au(1 1 1) electrode behavior in the neat ionic liquid and are beneficial to understanding in situ STM results involving surface morphological changes in such a media. 相似文献
59.
Shu Ping XU* Huan Wen CHEN Ai Min YU Qin Han JIN Hua Ying LIAO Changchun R&D Center for Analytical Instruments Department of Chemistry Jilin University Changchun Key Laboratory for Supramolecular Structure Spectroscopy of Ministr 《中国化学快报》2002,13(7):660-661
In recent years, the determination of Cr (VI) has attracted great attention because of its toxicity to human, plants and animals1-5. Usually, in the industrial waste water, the concentration of Cr (VI) is relatively high and should be determined frequently. So, an accurate, quick, and convenient method for the measurement of Cr (VI) in environmental water, as well as in river, lake, sea and tap water, is of great importance. The method for determination of Cr (VI) by diphenylcarbazine … 相似文献
60.
Alberto Bolognesi Chiara Botta Clara Mercogliano Marco Marinelli W. Porzio Luigi Angiolini Elisabetta Salatelli 《先进技术聚合物》2003,14(8):537-543
The degree of orientation of thin films of eight different polymeric structures, belonging to the class of soluble polyalkylthiophenes (PATs) has been studied. Thin films of the polymers, obtained by spin coating onto glass substrates, were oriented by means of the rubbing technique. The degree of orientation is related to the regioregularity of the system: highly regioregular polymers can be oriented, while regiorandom materials are not oriented. The degree of orientation can be improved by thermal annealing of the oriented films. As a result of annealing, which was performed at different temperatures according to the thermal behavior of the polymers, it was possible to increase the polarization ratio for poly(3-decylthiophene) up to 12–13 as detected from the UV-vis spectra in polarized light. Moreover in the investigated PATs, both the key role of molecular weight and its distribution for achieving a high orientation degree has been assessed. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献