Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt-Fe Alloy Electrocatalysts for Methanol Oxidation Performance

The designs of efficient and inexpensive Pt-based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen-doped carbon (NC) have been successfully prepared via co-engineering of the surface composition and electronic structure. The Pt₁Fe₃@NC/MWCNTs catalyst with moderate Fe³⁺ feeding content (0.86 mA/mg_Pt) exhibits 2.26-fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mg_Pt). Furthermore, the CO oxidation initial potential of Pt₁Fe₃@NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti-corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N-doped carbon (NC) layer, the Pt₁Fe₃@NC/MWCNTs catalyst presents an improved MOR performance and anti-CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.     

Fluoride effect on the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates

Fluorides promote the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates. The effect is more evident on the rate of the reaction at short reaction times, but a positive effect on selectivity is also observed under certain conditions. The effect is observed even under conditions under which chloride inhibits the reaction. Tetraethylammonium is a better countercation than sodium. Copyright © 2007 John Wiley & Sons, Ltd.     

Vapor-liquid equilibrium data at 25°C for six binary systems containing methyl acetate or methanol,with dichloromethane,chloroform, or 1,2-trans-dichloroethylene

Isothermal vapor-liquid equilibrium (VLE) data, at 25° C were determined by a saturation method for each of the six methanol or methyl acetate binary systems with dichloromethane, chloroform, and 1,2-trans-dichloroethylene. The experimental data satisfy the Redlich-Kister consistency test, and were correlated with five Gibbs free energy models. All the binary mixtures of methanol with the chlorinated compounds exhibit strong positive deviations from ideality while the mixtures of methyl acetate with the chlorinated compounds present negative deviations from ideal behavior.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Tandem silylformylation-allyl(crotyl)silylation: a new approach to polyketide synthesis

Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford β-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the ∼95° O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion.     

Assignments of methanol laser lines by frequency measurements and Fourier transform spectroscopy

We have measured the frequencies of four CH₃OH far-infrared laser lines that were previously known only by wavelength measurement. Two of these lines turned out to be doublets, bringing the total number of measured lines to six. We can now confirm the assignments of five of them and definitely disprove the assignments proposed for the sixth.In particular we confirm the assignments for the four strong laser lines at 205 and 208 µm pumped by the 9-P(34) CO₂ laser line. These lines share a common upper level in the first excited CO-stretch state, and terminate in the upper and lower levels of a hybrid state with J=5. Heterodyne frequency measurements and conventional microwave spectroscopy show that both lines are split into two components approximately 3.5 MHz apart. The origin of this further splitting is interpreted as a perturbed K-splitting.Work supported by Consiglio Nazionale delle Ricerche -Italia     

Synthesis of the ethyl ester of the mononitrile of malonic acid by the catalytic carbonylation of benzenesulfonyloxyacetonitrile

A new method has been developed for the synthesis of the ethyl ester of the mononitrile of malonic acid by the carbonylation of benzenesulfonyloxyacetonitrile in absolute ethanol in the presence of cobalt carbonyl. The yield of the desired product was 30% with 60–90% conversion of the starting compound. The effects of temperature, pressure, and reaction time were studied.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. S. M. Kirov Urals Polytechnical Institute, Ekaterinburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 215–216, January, 1992.     

Mössbauer study of nanodimensional nickel ferrite – mechanochemical synthesis and catalytic properties

Iron–nickel spinel oxide NiFe₂O₄ nanoparticles have been prepared by the combination of chemical precipitation and subsequent mechanical milling. For comparison, their analogue obtained by thermal synthesis is also studied. Phase composition and structural properties of iron–nickel oxides are investigated by X-ray diffraction and Mössbauer spectroscopy. Their catalytic behavior in methanol decomposition to CO and methane is tested. An influence of the preparation method on the reduction and catalytic properties of iron–nickel samples is established.     

甲醇与蓖麻油混合物运动粘度的实验研究

利用改型的乌别洛特毛细管粘度计,本文对243～353K温度范围内对质量配比为98.8:1.2的甲醇与蓖麻油混合物的运动粘度进行了实验研究,运动粘度测量结果的不确定度为1.06%,利用得到的实验数据拟合了甲醇 蓖麻油二元混合物的运动粘度方程.方程与实验数据最大偏差为3.31%,平均偏差为1.11%.     

顶空气相色谱法测定延生护宝液中甲醇残留量

本文用顶空气相色谱法，以ＧＤＸ－１０１为固定相，测定了延生护宝液中甲醇残留量，方法的回收率在８５．９％－１０１．６％之间，变异系数０．３％，最小检出量１．０ｍｇ／Ｌ。     

一种甲醇直接气相羰基化新催化剂

本世纪７０年代Ｍｏｎｓａｎｔｏ公司成功开发了甲醇液相羰化ＲｈＩ催化体系，使甲醇羰化生产醋酸成为重要的工业过程．然而，由于此工艺产物与催化剂分离复杂、铑资源紧缺以及体系中还必须加大量的碘甲烷（或氢碘酸）作促进剂，设备腐蚀严重．８０年代以来，甲醇气相羰...