Electrooxidation Mechanism of Methanol at Pt-Ru Catalyst Modified GC Electrode in Electrolytes with Different pH Using Electrochemical and SERS Techniques

The electrochemical and in-situ surface-enhanced Raman spectroscopy （SERS） techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon （Pt-Ru/GC） electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable.     

The theoretical basis of column chromatography in multicomponent separations. Part 2: Peak capacity. Column systems with good selectivity

The selectivity of a column system, S, defined by equation 28, includes a variation coefficient (β) of plate number with capacity ratio which has a large influence on the peak capacity, as shown in Fig. 18. Some typical chromatograms are given. In order to predict S for a column system from Kovat's Index, equations 40 and 41 are given to calculate the constant of the carbon number rule for squalane at different temperatures or for different stationary phases. The specific retention value of heptane on squalane at different temperatures can be calculated from equation 42. The nonpolarity index, defined by equation 43, was used to calculate the retention value of heptane on various stationary phases. In liquid chromatography, the order of elution may be reversed by changing the composition of the eluent on the same chemically bonded silica (manufactured in China). The linear relations between the log retention values of different kinds of solutes or of a single solute on the silicas of different surface areas when using the same eluent are given.     

无机纳米管材料合成进展

无机材料的微观结构决定了材料的许多特性,如传输行为、催化活性、分离效率、粘附、储存和释放动力学。具有管状结构纳米尺度的材料由于其特殊的结构及由此带来的特殊性能正成为一个令人兴奋的化学研究领域。文章综述了近年来无机纳米管材料的合成途径和进展。     

Determination of Y,Sm, Eu,Gd, Dy,Ho, Er in high purity terbium oxide by ICP-AES

Inductively coupled plasma atomic emission spectrometry (ICP-AES) was employed to determine Y, Sm, Eu, Gd, Dy, Ho and Er in high purity terbium oxide. Terbium oxide was dissolved in 0.5 mol/l HNO₃ and nebulized into the plasma generated by a 56 MHz RF generator at 1.5 kW output power. Using a Jobin-Yvon 1-m Czenry-Turner high resolution, high dispersion scanning monochromator, lines mutually interference-free as well as free of interference from the matrix Tb were chosen for the seven analytes. A set of standards containing the analytes in the concentration range 0.01–1.0 gmg/ml with 1 mg/ml Tb was used for calibration. It was necessary to apply background correction to the gross analyte line intensities in order to obtain linear calibration plots for the analytes.     

Flow injection analysis methods for determination of diffusion coefficients

Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W_1/2) with the diffusion coefficient (D_m) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a D_m value of 0.72 × 10⁵ cm² s⁻¹ was found versus a literature value of 0.76 × 10⁵ cm² s⁻¹ (error, 5%). For potassium hexacyanoferrate (II) a D_m value of 0.67 × 10⁵ cm² s⁻¹ was obtained versus a literature value of 0.63 × 10⁵ cm² s⁻¹ (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 10⁵ D_m/cm² s⁻¹ are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.     

示波极谱法测定地质样品中痕量氟

提出了地质样品经半熔法分解后,8-羟基喹啉沉淀干扰组分,过量的8-羟基喹啉用四氯化碳萃取分离,在六次甲基四胺缓冲液中测定Ce(Ⅲ)-ALC-F~-络合吸附波。并对标准物质中F~-进行测定,其测定值与推荐值吻合。方法的RSD为5.6％,检出限为0.6μg·g~(-1)。     

Repeat Space Theory Applied to Carbon Nanotubes and Related Molecular Networks. I

The present article is the first part of a series devoted to extending the Repeat Space Theory (RST) to apply to carbon nanotubes and related molecular networks. Four key problems are formulated whose affirmative solutions imply the formation of the initial investigative bridge between the research field of nanotubes and that of the additivity and other network problems studied and solved by using the RST. All of these four problems are solved affirmatively by using tools from the RST. The Piecewise Monotone Lemmas (PMLs) are cornerstones of the proof of the Fukui conjecture concerning the additivity problems of hydrocarbons. The solution of the fourth problem gives a generalized analytical formula of the pi-electron energy band curves of nanotube (a, b), with two new complex parameters c and d. These two parameters bring forth a broad class of analytic curves to which the PMLs and associated theoretical devices apply. Based on the above affirmative solutions of the problems, a central theorem in the RST, called the asymptotic linearity theorem (ALT) has been applied to nanotubes and monocyclic polyenes. Analytical formulae derived in this application of the ALT illuminate in a new global context (i) the conductivity of nanotubes and (ii) the aromaticity of monocyclic polyenes; moreover an analytical formula obtained by using the ALT provides a fresh insight into Hückel’s (4n+2) rule. The present article forms a foundation of the forthcoming articles in this series. The present series of articles is closely associated with the series of articles entitled ‘Proof of the Fukui conjecture via resolution of singularities and related methods’ published in the JOMC.     

碳纤维表面酰氯化及其与尼龙6的接枝Ⅰ、接枝方法及复合材料的力学性能

碳纤维表面酰氯化及其与尼龙6的接枝Ⅰ、接枝方法及复合材料的力学性能;阴离子接枝     

V. Thioanalogues of sparteine lactams. (+)-2-Thiono-17-oxosparteine and (+)-2,17-dithionosparteine

The X-ray and spectroscopic results clearly indicate that the (+)-2-thiono-17-oxosparteine (1) and (+)-2,17-ditihionosparteine (2) are conformationally rigid. In order to analyze deviations of lactam/thiolactam groups from planarity induced by ring constraints, the Dunitz-Winkler approach has been used. The lactam and thiolactam groups are close to planarity, only the lactam group in one of the two independent molecules of 1 is markedly non-planar. The bond angles in the thiolactam and lactam groups are highly diverse. Rings A and C adopt a distorted sofa conformation in both compounds. The distortions in the molecules of 2 as compared with those in the related monothiolactams correspond to the unusual chemical shifts of H5(eq), H5(ax) and H11, as well as to the extremely low J_5ax-6 and extremely large J_5eq-6 coupling constants. Also chemical shifts show a similar regularity being extremely high and low for C2 and C17, respectively.     

Crosslinking of vinyl‐terminated biphenyl and naphthalene side‐chain liquid‐crystalline poly(epichlorohydrin) derivatives

We performed the crosslinking of vinyl‐terminated biphenyl and naphthalene side‐chain liquid‐crystalline polyethers using peroxide‐type initiators with and without the addition of tertiary amine promoters. The crosslinking temperatures were chosen in the range of mesophase stability to allow the mesophase order to be frozen. The biphenyl derivatives, with a high isotropization temperature, were crosslinked to a large extent. This led to anisotropic thermosets. To crosslink naphthalene derivatives, amine promoters were needed, but degrees of crosslinking were lower, and anisotropic elastomers were obtained. Crosslinking processes were studied by differential scanning calorimetry, polarized optical microscopy, and Fourier transform infrared spectroscopy. The nature of the frozen mesophase was confirmed by X‐ray diffraction studies on mechanically oriented samples. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2237–2244, 2002