超高比表面炭载钼煤气甲烷化催化剂

以沥青中间相为原料，氢氧化钾直接活化，获得了比表面达２３６３ｍ￣２／ｇ的超高比表面炭分子筛（ＣＭＳ）。分别以ＣＭＳ、ＳｉＯ＿２、活性炭和θ－Ａｌ＿２Ｏ＿３为担体，制备了负载钼催化剂，并研究其加压甲烷化反应性能，发现活性依下面顺序增加：θ－Ａｌ＿２Ｏ＿３＜ＳｉＯ＿２＜活性炭（ＡＣ）＜ＣＭＳ。还分别以钼酸铵和磷钼酸（ＨＰＭｏ）为前驱体，制备了ＣＭＳ负载钼催化剂，并考察了其煤气甲烷化活性，发现不同的催化剂前驱体对催化剂反应活性影响很大。根据产物中ＣＨ＿４／ＣＯ＿２的变化，推测ＣＯ在钼催化剂上的甲烷化反应包括如下两个步骤：（１）３Ｈ＿２＋ＣＯ→ＣＨ＿４＋Ｈ＿２Ｏ，（２）ＣＯ＋Ｈ＿２Ｏ→ＣＯ＿２＋Ｈ＿２。     

Determination of Diffusion Coefficients for Binary Nonelectrolyte Mixtures. A Free-Volume Predictive Approach

A diaphragm cell has been used to measure mutual diffusion coefficients at 25°C for four binary nonelectrolyte mixtures: ethylbenzene + n-hexane, carbon tetrachloride + ethylbenzene, cyclohexane + p-xylene, and 1,2-dichloroethane + cyclohexane. A free-volume predictive approach for binary mutual diffusion coefficients was developed and tested. Only infinite dilution diffusion coefficients, some readily available pure substance data, and UNIFAC group contribution parameters are used in the model. No binary equilibrium thermodynamic information is required. For 73 binary systems with an overall average absolute deviation of 5.2%, it has been shown that the developed method is better than two commonly available reference methods for the prediction of liquid diffusion coefficients.     

单核零价过渡金属配合物的研究——Ⅱ.含有π-键合醌及双齿氮配体的混配零价钯配合物的合成与表征

本工作合成了一系列十个新的零价钯混配配合物,并对这些配合物进行了表征.研究了配体的立体效应和电子效应的差别,讨论了配体间的相互作用.一.配合物的合成与组成据文献合成dba(PhCH=CHCOCH=CHPh)和Pd_2(dba)_3(CHCl_3).其余试剂及溶剂均为市售商品,用前经无水无氧处理.     

A Study of the Silylation of 1,8-Dihydroxynaphthalene

Twelve compounds each having a six membered Si-contained heterocycle, have been successfully synthesized. Of these eleven compounds have never been reported in the literature. The structures were confirmed by Spectral analysis and elementary analysis. The stability and properties of these compounds is also discussed.     

以有机镍配合物为前体制备担载镍催化剂的研究

描述了以镍单核配合物ＮｉＣｐ２和簇合物Ｎｉ３Ｃｐ３Ｎ－ｔ－Ｃ４Ｈ９为前体的ＳｉＯ２载镍催化剂的制备，通过元素分析、ＴＲＲ、ＴＰＤＥ、ＸＰＳ，ＣＯ吸附和苯加氢反应对以镍配合物和簇合物为前体制备的催化剂的性能及其制备过程了研究和表征。结果表明，镍与合物和簇合物在担载过程中同载体ＳｉＯ２表面发生了相互作用，其化学组成发生了变化，在苯加氢反应中，此催化剂的活性比以Ｎｉ（ＮＯ３）２为前体制备的催化剂高得多，     

药物分子在玻碳电极上的电分析化学研究──Ⅴ．安乃近的伏安行为及测定

提出了一种测定安乃近新法。由于安乃近没有电活性，故将安乃近和盐酸在１００℃共热后生成电活性产物，用玻碳电极在０．１ｍｏｌ／ＬＮａＯＨ中得一良好的阳极氧化伏安峰，Ｅｐ＋０．３５Ｖ（ｖｓ·Ａｇ／ＡｇＣｌ）左右，峰电流与安乃近浓度在０．１～１００ｍｇ／Ｌ之间呈线性关系，分析了制剂安乃近的含量，实验证实电极反应属于扩散控制的不可逆过程。     

锰（Ⅱ）—邻菲口罗啉配合物极谱吸附波及其应用

在ｐＨ９．５ＮＨ３ＮＨ４Ｃｌ缓冲溶液中，Ｍｎ（Ⅱ）与邻菲口罗啉形成的配合物在－１．３６Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的吸附波，一阶导数峰电流与Ｍｎ（Ⅱ）浓度在５×１０－８５×１０－６ｍｏｌ／Ｌ范围内呈线性关系，检出限为２×１０－８ｍｏｌ／Ｌ对极谱性质及反应机理进行了研究，用该法测定了大豆和茶叶中的微量锰，结果满意     

Chemical Constituents from the Stems of Mahonia Japonica

A new dihydroberberine alkaloid, 7,8‐dihydro‐8‐methoxyberberine ( 1 ), along with six known compounds including two dihydroberberine alkaloids, 7,8‐dihydro‐8‐hydroxyberberine ( 2 ) and oxyberberine ( 3 ) and four protoberberine alkaloids, berberine ( 4 ), palmatine ( 5 ), jatrorrhizine ( 6 ) and columbamine ( 7 ), were isolated from the stems of Mahonia japonica. These compounds were characterized and identified by physical and spectral evidence.     

两个含有平行交替链的新型二氰胺配位高聚物: {Mn(dmpz)[N(CN)2]2}2和{Cu(dmpz)[N(CN)2]2}2

Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.     

Geometries and properties of bimetallic phosphido-bridged complex Cp(CO)2W(μ-PPh2)W(CO)5 and Cp(CO)3W(μ-PPh2)W(CO)5

Complete geometry optimizations were carried out by HF and DFT methods to study the molecular structure of binuclear transition-metal compounds (Cp(CO)₃W(μ-PPh₂)W(CO)₅) (I) and (Cp(CO)₂W(μ-PPh₂)W(CO)₅) (II). A comparison of the experimental data and calculated structural parameters demonstrates that the most accurate geometry parameters are predicted by the MPW1PW91/LANL2DZ among the three DFT methods. Topological properties of molecular charge distributions were analyzed with the theory of atoms in molecules. (3, −1) critical points, namely bond critical point, were found between the two tungsten atoms, and between W1 and C10 in complex II, which confirms the existence of the metal–metal bond and a semi-bridging CO between the two tungsten atoms. The result provided a theoretical guidance of detailed study on the binuclear phosphido-bridged complex containing transition metal–metal bond, which could be useful in the further study of the heterobimetallic phosphido-bridged complexes.