Ni,Pd／Al2O3对丙酮加氢一步合成甲基异丁基酮性能比较

研究了Ａｌ２Ｏ３负载Ｎｉ、Ｐｄ催化剂上丙酮加氢一步合成甲基异丁基酮的反应活性。考察了不同Ｎｉ含量和不同Ｐｄ含量对活性的影响。结果表明，在载体Ａｌ２Ｏ３中加入不同含量的ＳｉＯ２后，会改善载体的性能，Ｎｉ／Ａｌ２Ｏ３催化剂中添加稀土元素Ｌａ或Ｃｅ后可改善催化剂的稳定性。     

对固体圆二色光谱测试方法的再认识——兼谈“浓度效应”

对近期发展的固体圆二色(CD)光谱测试方法进行了概述、评价和比较, 着重探讨了“浓度效应”的存在使固体CD光谱失真的原因. 通过对本课题组和其他作者已报道的四种化合物的固体CD谱再测试的反思, 强调了依手性化合物的手性光谱学性质不同, 根据浓度梯度实验选择其合适测试浓度的必要性. 对固有手性的阻转异构化合物(S)-1,1'-联二萘酚(S-BINOL)进行了成膜法固体CD谱浓度梯度测试, 发现所得固体薄膜CD谱中也存在着“浓度效应”     

Synthesis and Crystal Structure of a Novel Layered Lead(Ⅱ) Carboxylate-sulfonate Compound Templated by 4,4''-Bipyridine

A new lead(Ⅱ) carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group P,(1) with a=8.1573(6), b=9.4663(7), c=12.7488(9) (A), α=89.2320(10), β=80.7380(10), γ=77.9760(10)°, Z=2, V=950.10(12) (A)3, Mr=599.57, Dc=2.096 g/cm3, μ=9.032 mm-1, F(000)=572, the final R=0.0412 and wR=0.1035. It has a 1D chain structure, and the Pb(Ⅱ) is six-coordinated. Two PbO6 polyhedra are interconnected via edge-sharing into a two-core unit. Such units are further interconnected by 3-sulfonato-benzoic acids into 1D chains which are linked by hydrogen bonds into a layer structure. The 4,4'-bipyridines are located at the interlayer space and link the layers into a supramolecular structure by π-π stacking interactions.     

CC14法合成α—羟基—α—甲基苯丙酮的研究

α 羟基 α 甲基苯丙酮 (ＰＨＭＰ)是一种性能优良的新型光引发剂 ,具有引发效率高、热稳定性好、耐黄变、无异味等优点[1,2 ] 。现有合成方法步骤多 ,产率低 ,后处理麻烦 ,操作复杂[3,4] ,且在反应过程中会产生ＨＣ1或ＨＢｒ等有毒副产物。本文研究了在相转移催化剂的作用下[5,6 ] ,ＣＣｌ4直接氯化水解生成α 羟基 α 甲基苯丙酮的新方法。该方法不仅减少了反应步骤 ,简化了操作 ,而且提高了产品质量。1　实验部分1 .1　仪器与试剂傅立叶红外光谱仪Ｐｅｒｋｉｎ Ｅｌｍｅｒ 1 71 0 ,ＷＸＳ 1型阿贝折光仪。异丁酸 ,ＳＯＣｌ2 ,苯 ,四氯化…     

制备参数对Au／Fe2O3催化剂水煤气变换性能的影响

 采用共沉淀法制备了Au／Fe2O3催化剂，并系统地考察了制备参数对其催化WGS性能的影响．通过BET，XRD，XRF，H2－TPR和HRTEM等表征手段，初步考察了Au／Fe2O3催化剂具有高催化活性的原因．结果表明，金负载量、沉淀剂种类、沉淀方式、沉淀pH值、焙烧气氛和焙烧温度对Au／Fe2O3催化剂的催化性能均具有较大的影响．Au／Fe2O3催化剂的低温高活性是纳米Au与Fe3O4协同作用的结果；Au／Fe2O3催化剂的高温活性是由于活性相Fe3O4起主要作用的结果．纳米Au粒子的烧结会降低其催化活性．     

α－芳甲酰基烯酮二硫缩醛的新合成方法

以碳酸钾为碱，芳甲酰丙酮（１）与二硫化碳、卤代烃反应得到２－乙酰基－２－芳甲酰基烯酮硫代缩醛（２），２在乙硫醇钾作用下脱乙酰基生成标题化合物（３）。１→３的转化具有反应条件温和、产物产率高及对３中各种缩醛基均可通用等特点。     

均相催化反应在任一给定形状微电极上的稳态电化学行为

根据反应层的概念对在任一给定形状微电极上进行的准一级和二级均相催化反应机理(EC'')的稳态电化学行为进行了研究。本方法简便易行,不需要解复杂方程的数学技巧。利用推导出的这些方程,可计算准一级和二级均相催化反应的动力学常数。     

若干中性配体对Mo—Fe—S簇合物自兜的影响

通过电子吸收光谱的变化研究了一些含N和含P中性配体对MoS_4~(2-)-nFeCl_2-DMF体系形成立方烷型Mo-Fe-S簇合物的可能影响。     

傅立叶变换红外光谱法对聚氯乙烯及邻苯二甲酸酯类增塑剂的快速鉴定

应用傅立叶变换红外光谱法实现了聚氯乙烯及邻苯二甲酸酯类增塑剂的快速鉴别。对聚氯乙烯的定性采用了衰减全反射技术,用锗作为晶体材料,对邻苯二甲酸酯类的定性则采用透射法。用溶解-沉淀法对试样进行分离和纯化,所用溶剂为四氢呋喃,沉淀剂为无水乙醇。经过此方法,聚合物与增塑剂达到很好的分离和纯化。     

Theoretical investigation of the decarbonylation of acetaldehyde by Fe+ and Cr+.

We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521].