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41.
为了在分子层次上揭示相关催化反应的机理, 人们对过渡金属氧化物团簇与碳氢化合物分子反应进行了大量研究. 相比于过渡金属氧化物团簇阳离子, 阴离子对一些碳氢化合物的活性弱得多, 因此研究还很少. 在本工作中, 我们通过激光溅射产生钒氧团簇阴离子VxOy, 产生的团簇在接近热碰撞条件下与烷烃(C2H6和C4H10)以及烯烃(C2H4和C3H6) 在一个快速流动反应管中进行反应, 飞行时间质谱用来检测反应前后的团簇分布. 在VxOy与烷烃的反应中, 生成了产物V2O6H-和V4O11H-; 在与烯烃的反应中, 产生了相应的吸附产物V4O11X-(X=C2H4或C3H6). 密度泛函理论计算表明: V2O-6和V4O-11可以活化烷烃(C2H6和C4H10)的C—H键, 也可以与烯烃(C2H4和C3H6)发生3+2环化加成反应形成一个五元环结构(-V-O-C-C-O-), C—H键活化与环加成反应都需经历可以克服的反应能垒. 理论计算与实验观测结果相符合. V2O-6和V4O-11团簇都具有氧原子自由基(O·或O-)的成键特征, 活性O-物种也经常出现在钒氧催化剂表面, 因而本研究在分子水平上, 揭示了表面活性氧物种与碳氢化合物反应的机理. 相似文献
42.
By the use of time domain reflectometry method, dielectric measurements were carried out on dimethylformamide‐2‐nitrotoluene solvent mixtures in the frequency range 10 MHz‐20 GHz, at various temperatures from 15 °C to 45 °C. These solvent mixtures as well as pure solvents display a Debye type dispersion. Their frequency dependent dielectric properties can be summarized by the three parameters in the Debye equation: a static permittivity, permittivity at high frequency and a dielectric relaxation time constant. The free energy of activation for dipolar relaxation process and the Kirkwood correlation factor were determined using these fitting parameters for these solvent mixtures at various concentrations and temperatures. By using these dielectric parameters, the excess permittivity and excess inverse relaxation time is obtained. The excess permittivity is found to be positive for all concentrations and temperatures whereas the excess inverse relaxation time is negative. 相似文献
43.
A method is described for the simultaneous quantitative determination of monoamines and related compounds from urine and brain tissue samples in the pg-range, using a GC/MF instrument LKB-2091 provided with a multiple ion detection (MID) system and capillary columns. The simultaneous detection of “fingerprints” with fourteen and more compounds during one single GC run was achieved after the intoduction of “time gates” for the detection of the different characteristic masses. Several modifications to the LKB equipment permitted exact reproducibility of retention times, which is essential for the use of “time gates”. The detection of “fingerprints” with these acidic, basic and alcoholic substances was achieved by the extraction of the dried biological samples with silylating agents. 相似文献
44.
Hiroyuki?OhshimaEmail author Hiroko?Sato Hiroki?Matsubara Atsushi?Hyono Masayoshi?Okubo 《Colloid and polymer science》2004,282(10):1174-1178
A theory of adsorption kinetics with time delay [Ohshima et al. (1992) Colloid Polym. Sci. 270:707] is developed and applied to the surface tension of a polymer solution. It is found that the general appearance of the overshoot and oscillation in the time course of the surface tension of aqueous gelatin solution observed by Sato and Ueberreiter [(1979) Makromol. Chem. 180:829, 1107; (1979) Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 20:907) can be explained by the present theory. 相似文献
45.
近年来亚硝酸甲酯分子(CHa0NO)的光解动力学研究十分活跃{‘5],主要集中在紫外激光的单光子解离的机理,光解过程的矢量相关性质和光解产物的态分布.CH30NO分子的解离能D。(CH30-NO)=174kJ·mol‘,若单从能量上看,人<689。的光就能使其解离,但人>400urn的光解离研究还未见报导.*H30*0分子在人>40onm的强激光场下是充电离还是先解离,是单光子解离还是多光子解离,以及通过哪个电子态解离都不清楚.时间飞行质谱不仅具有质量分辨率高、范围宽,而且响应快,因此适合做光解光电离过程初生态产物的探测.特别是时间飞… 相似文献
46.
《Analytical letters》2012,45(12):2003-2011
It is difficult to determine sulfur-containing volatile organic compounds in the atmosphere because of their reactivity. Primary off-line techniques may suffer losses of analytes during the transportation from field to laboratory and sample preparation. In this study, a novel method was developed to directly measure dimethyl sulfide at parts-per-billion concentration levels in the atmosphere using vacuum ultraviolet single photon ionization time-of-flight mass spectrometry. This technique offers continuous sampling at a response rate of one measurement per second, or cumulative measurements over longer time periods. Laboratory prepared samples of different concentrations of dimethyl sulfide in pure nitrogen gas were analyzed at several sampling frequencies. Good precision was achieved using sampling periods of at least 60 seconds with a relative standard deviation of less than 25%. The detection limit for dimethyl sulfide was below the 3 ppb olfactory threshold. These results demonstrate that single photon ionization time-of-flight mass spectrometry is a valuable tool for rapid, real-time measurements of sulfur-containing organic compounds in the air. 相似文献
47.
A simple, quick and novel method for the determination of diffusion properties through polymer films, based on Quantum Resistive Sensors made of Conductive Polymer nanoComposites is presented. The integral time lag method is employed for the calculation of diffusion coefficient, and the results are compared simultaneously with that of Fourier transform infrared spectroscopy and sorption method. Two model polymers, a semi‐crystalline poly(lactic acid) and an amorphous poly(isobutylene‐co‐isoprene), are used to validate the study. A good correlation is established between the diffusion coefficient values derived from all techniques demonstrating the interest of such reliable, simple and cheap nanosensors for the quick determination (several minutes) of diffusion properties in polymer films. Our first results suggest that this technique is meaningful for the determination of barrier properties in nanocomposite membranes filled with platelets of graphene or clay. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
48.
《Stochastics An International Journal of Probability and Stochastic Processes》2013,85(3-4):207-226
In the present paper, a framework for parametric estimation in nonlinear time series is developed. Strong consistency and asymptotic normality of minimum Hellinger distance estimates for a determined class of nonlinear models are investigated. The main Interest for these estimates is motivated by their robustness under perturbations as it has been emphazized in Beran [2]. The first part of the paper is devoted to the study of some probabilistic properties which ensure the existence and the optimal properties of the estimates 相似文献
49.
We present a study of time-delay effects on a two-actor conflict model based on nonlinear differential equations. The state of each actor depends on its own state in isolation, its previous state, its inertia to change, the positive or negative feedback and a time delay in the state of the other actor. We use both theoretical and numerical approaches to characterize the evolution of the system for several values of time delays. We find that, under particular conditions, a time delay leads to the appearance of oscillations in the states of the actors. Besides, phase portraits for the trajectories are presented to illustrate the evolution of the system for different time delays. Finally, we discuss our results in the context of social conflict models. 相似文献
50.
《Optimization》2012,61(5-6):361-385
We present three counterexamples related to the maximum principle for the time optimal problem. The system is linear, infinite dimensional, with point target and “full” control 相似文献