CO吸附在过渡金属铂表面的微观动力学研究

建立了处理双原子分子-表面相互作用的推广的LEPS势.借助推广的LEPS势,系统研究了一氧化碳分子在铂低指数表面吸附的动力学特性,重现了低指数表面的分子吸附热、吸附几何及本征振动等实验数据；鉴定了某些不合理的文献信息,预测了实验尚未探测到的重要信息:预测到Pt(100)表面四重洞位的C－O伸缩振动频率为1 962.60 cm－1;预测到Pt(110)表面吸附态的C－O及C－Pt键长分别为115.1、147 pm.     

碳纳米管电极超大容量离子电容器交流阻抗特性

采用碳纳米管作为超大容量离子电容器的电极材料,应用交流阻抗频谱法,研究了超大容量离子电容器的频率响应特性.结果表明,用碳纳米管块作电极,超大容量离子电容器在频率250 mHz以下出现“电荷饱和”；而用活性炭块作电极, 超大容量离子电容器在频率为100 mHz时仍未出现“电荷饱和”,这说明碳纳米管电极超大容量离子电容器的频率响应特性优于活性炭电极超大容量离子电容器的频率响应特性.上述两类超大容量离子电容器的阻抗谱中均出现倾角约为45°的直线段,其相位角均远小于理想电容器的相位角90°.     

Comparative EIS study of a paste electrode containing zinc powder in neutral and near neutral solutions

The corrosion and passivation of Zn powder particles dispersed in a paste electrode immersed in 0.5 M Na₂SO₄ and 5×10^–3 M Na₂HPO₄ solutions were studied mainly by electrochemical impedance spectroscopy. The role played by diffusion in the mechanism of anodic oxidation of zinc powder particles has been shown. It was demonstrated that the anodic reactionof Zn powder in neutral or near neutral media involves at least two adsorbed intermediates. By simulating the porous structure of the electrode, some information about porous nature of zinc electrode could be extracted. Electronic Publication     

Hydrogen transport through Pd-Ni alloy electrodeposited on Pd substrate

Hydrogen transport through a Pd-Ni alloy electrodeposited on a Pd substrate (Pd-Ni/Pd bilayer symmetric electrode) has been investigated using cyclic voltammetry and a.c. impedance spectroscopy combined with the electrochemical hydrogen permeation method. The permeation build-up current transients and the measured impedance spectra were analyzed using the time-lag method for the bilayer electrode and a complex non-linear least squares data-fitting method based upon the derived Faradaic admittance for the hydrogen absorption into and diffusion through the bilayer electrode under the permeable boundary condition, respectively. The value of the hydrogen diffusivity in the Pd-Ni layer was lower than that in the Pd layer. Furthermore, the values of the charge transfer resistance and equilibrium absorption constant for the Pd-Ni/Pd bilayer electrode were higher than those for the Pd single layer electrode. From the experimental results, the role of the thin Ni(OH)₂ film formed on the Pd-Ni layer surface in the hydrogen transport through the Pd-Ni/Pd bilayer electrode is discussed in terms of its passivating effect and extremely large hydrogen solubility. Received: 22 January 1997 / Accepted: 15 April 1997     

后交联型St-DVB大孔吸附树脂对低级醇类的吸附性能研究

分别在静态和动态条件下研究了Friedel—Crafs后交联型聚苯乙烯-二乙烯基苯(St-DVB)大孔吸附树脂对水溶液中多种低级一元醇的吸附性能，测定静态吸附等温线和动态吸附曲线，并分别按照Langmuir和Freundlich模型进行拟合．结果显示，树脂对水中低浓度低级一元醇的吸附过程属于放热的物理吸附过程，树脂吸附能力随着一元醇碳原子数的增加，即分子内疏水基团质量的增加而增加；树脂对直链醇的吸附能力稍强于同分异构的支链醇．     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

Determination of estrogenic steroids in surface water and wastewater by liquid chromatography-electrospray tandem mass spectrometry

An analytical method is presented which permits trace level determination of 17alpha-ethynylestradiol (EE2), 17beta-estradiol (E2), and estrone (E1). Using this method, the estrogenic steroids were analyzed in drinking water, surface water, and wastewater (sewage influents and effluents) at concentrations down to 0.1 ng/L. Sample volumes between 100 and 500 mL are concentrated using automated solid-phase extraction. Analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Applying simple clean-up procedures and internal standard calibration, recovery losses resulting from matrix-dependent ion suppression during electrospray ionization could be compensated for all of the investigated compounds. Recoveries around 100% were obtained for all analytes after correction using the internal standards. Limits of quantification (LOQ) were between 0.1 and 0.4 ng/L for purified sewage, surface, ground, and drinking water and between 1 and 2 ng/L in the case of raw sewage. Water treatment by wastewater treatment plants (WWTPs) or by a surface water treatment plant affected the removal of all estrogenic steroids. Thus, E1, E2, and EE2 were removed in the municipal WWTPs to the extent of 93%, 93%, and 80%, respectively. In the effluents of the WWTP in Ruhleben (Berlin, Germany), E1, E2, and EE2 were detected at the low ng/L level. E2 and EE2 were, however, not present in the Berlin surface water above the LOQ (0.2 ng/L). E1 was the only compound that could be detected in surface water samples. After additional surface water treatment it was still detectable but only at trace-level concentrations with a mean value of 0.16 ng/L.     

Low Mach number limit of inviscid Hookean elastodynamics

The low Mach number limit of inviscid Hookean elastodynamic equations is rigorously proved in bounded domain, whole space and periodic domain, respectively. The uniform existence of smooth solutions and convergence results as the Mach number tends to zero are obtained in three different domains.     

A Systematic Evaluation of Polyurethane as a Conformal Coating for the Inhibition of Corrosion on Electronic Components

The corrosion of printed circuit boards can be effectively prevented with a polyurethane conformal coating. In this study, the protective performance of PU coating was investigated systematically through electrochemical measurements and simulated exposure/immersion tests. Some fungi tests were also included. All experimental results show that a polyurethane coating effectively inhibits corrosion on printed circuit boards. The optimal thickness of the coating film should be about 60 μm. Long-term exposure tests showed that this coating material could preserve the reliability of the investigated printed circuit boards for more than 400 days in a 90% relative humidity environment at 25°C.     

In situ prepared polypyrrole for low humidity QCM sensor and related theoretical calculation

In situ preparation of polypyrrole (Ppy) by photo-polymerization coated on a quartz crystal microbalance (QCM) as a low humidity sensor was reported. Different concentrations of Ppy films say 0 wt.% (as blank), 0.1, 1, and 10 wt.% were investigated to measure humidity concentrations between 14.7 and 5412.5 ppm_v. The adsorption/desorption behavior was also examined at humidity concentration 510.2 ppm_v. The sensitivities of 0, 0.1 and 1 wt.% Ppy films at 51.5 ppm_v were 0.143, 0.219 and 0.427, respectively. For 1 wt.% Ppy, the highest sensitivity was obtained. The slope and correlation coefficients (R²) for 1 wt.% Ppy at the ranges of 14.7–898.6 ppm_v were 0.0646 and 0.9909, respectively. A series of molecular simulations have been carried out to calculate bond energy for the water molecule interaction with Ppy, which was found to be 3 kcal/mol indicating the existence of hydrogen bonding during the sorption process. Based on Langmuir isotherm adsorption assumption, for 0.1 and 1 wt.% Ppy films, the association constants were 2606.30 and 5792.98, respectively. This larger association constant for 1 wt.% Ppy film explains higher sensitivity.