Surface Structure and Catalytic Performance of CuCl/SiO2-Al2O3 Catalysts for Methanol Oxidative Carbonylation

Aluminum was doped into amorphous silica gel to modify its surface structure. The obtained SiO₂-Al₂O₃ support was used to prepare the CuCl/SiO₂-Al₂O₃ catalyst by solid-state ion exchange, and the catalyst activity for liquid-phase oxidative carbonylation of methanol to dimethyl carbonate was investigated. The results showed that the prepared SiO₂-Al₂O₃ support kept the amorphous structure of the silica gel. The BET specific surface area of the silica gel was decreased to 200 m²/g, and the surface acid sites (including Brønsted acid sites) were increased. In the CuCl/SiO₂-Al₂O₃ catalyst, CuCl was not only dispersed on surface but also was ion exchanged with surface Brønsted acid sites of the SiO₂-Al₂O₃ support to form Cu⁺ species, which resulted in a decrease in BET specific surface area to 148 m²/g. These two kinds of Cu⁺ species on the catalyst surface were both active centers for the oxidative carbonylation of methanol to dimethyl carbonate. When the catalyst was prepared with Si/Al molar ratio of 5 and was calcined at 500 °C, the selectivity and space-time yield of dimethyl carbonate reached 74% and 1.27 g/(g·h), respectively.     

CuO/SBA-15催化剂上巴豆醛选择性加氢

通过γ-氨丙基三甲氧基硅烷(APTS)偶联与Cu2 离子络合两步法将CuO负载到介孔分子筛SBA-15上,制得CuO/SBA-15催化剂,考察了催化剂的巴豆醛选择性加氢反应性能.通过X射线粉末衍射、氮气吸脱附和程序升温还原(TPR)技术对催化剂进行了表征.结果表明,SBA-15分子筛负载CuO后保持原有的介孔结构,但是孔容和比面表积随着CuO负载量的增大而下降.TPR结果表明CuO/SBA-15系列催化剂有三种CuO物种:高分散CuO、晶相CuO和进入SBA-15分子筛骨架的Cu2 .高分散CuO物种对巴豆醛加氢反应的催化活性最高,晶相CuO物种次之,而进入SBA-15分子筛骨架的Cu2 物种几乎没有活性.     

Synthesis and Structure of a La（Ⅲ） Complex of 1,10-Phenanthroline-2,9-dicarboxylate： a Three-dimensional Network via Hydrogen Bonding Interactions

A new La（Ⅲ） complex, {[La（L）（NO3）（H2O）3]·H2O}n （L = 1,10-phenanthroline- 2,9-dicarboxylate）, has been synthesized and structurally determined by X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P21/c with a = 7.7358（17）, b = 8.1664（18）, c = 28.271（6） A, β= 95.184（4）°, V= 1778.6（7） A3, Z = 4, C14H14LaN3O11, Mr = 539.19, Dc = 2.014 g/cm^3, μ= 2.471 mm^-1, F（000） = 1056, the final R = 0.0350 and wR = 0.0659. In this complex, each metal center adopts a ten-coordination geometry formed by two N atoms from a ligand L and eight O atoms from three H2O molecules, a nitrate ion and carboxylates of two ligands. Each ligand adopts a N2,O3-pentdentate coordination mode using two N and two O atoms chelating a La（Ⅲ）, and using another O atom of carboxylate to bridge another La（Ⅲ） center resulting in a 1D helical chain molecule. Intermolecular strong O-H…O and weak C-H…O hydrogen bonds extend the 1D chain structure into a 3D supramolecular architecture.     

2-(2-甲基烯丙基)-3-(3-甲基-1,2-丁二烯基)环己-2-烯酮重排生成八元环化合物反应机理的理论研究

采用密度泛函理论B3LYP/6-31G(d,p)方法研究了2-(2-甲基丙烯基)-3-(3-甲基-1,2-丁二烯基)环己-2-烯酮重排生成八元环化合物在气相中的反应机理. 考虑了两条可能的反应途径: 途径1包含5个过程, 途径2包含两个过程. 从能量上看, 两条途径的决定速度步均是[1,5]氢迁移. 采用自洽反应场极化连续模型(PCM模型)和极化导体模型(CPCM模型)研究了反应体系在甲苯溶液中的溶剂效应. 结果表明, 气相和溶液中途径2均是较优途径, 并且甲苯对该反应的溶剂化效应不明显. 理论研究结果与实验观察结果一致, 并很好地解释了有关实验现象.     

基于温敏水凝胶的可调胶体晶体制备

基于单分散胶体粒子悬浊液在温敏水凝胶表面可以形成湿润型胶体晶体的现象, 利用温敏水凝胶对水的控释作用制备了温度敏感的可调制胶体晶体. 在室温下利用提拉法在温敏水凝胶聚N-异丙基丙烯酰胺(PNIPAAm)表面制备湿润型胶体晶体膜. 由于胶体粒子的有序排列, 胶体晶体显示出一个尖锐的反射峰. 当温度上升到34 ℃以上时, 由于PNIPAAm水凝胶中的水被释放, 导致胶体晶体中粒子浓度降低, 粒子间距增加; 反射峰发生红移. 这些特性可以通过温度变化进行调制.     

聚苯胺钡铁氧体纳米复合材料的制备、表征及性能

采用原位掺杂聚合法, 将聚苯胺(PANI)对粒径在60~80 nm的M型钡铁氧体颗粒(BaFe12O19)进行了包覆, 得到了具有棒状结构的复合材料. 通过X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等测试手段对材料的形貌和结构进行了表征. 结果表明, PANI链段与BaFe12O19颗粒之间存在作用力. 使用振动磁强计和四探针法测定了复合材料的磁性能与电性能后发现, 饱和磁化强度与矫顽力均随聚苯胺含量的增加呈规律性下降趋势, 而电导率呈上升趋势. 复合材料的吸收特性测试结果表明, 该材料反射率小于-20 dB时, 带宽可以达到15.07 GHz. 同时详细地讨论了纳米复合材料的聚合机理及相互作用.     

氯过氧化物酶修饰电极对一氯二甲酮的催化氯化

通过将氯过氧化物酶溶液(Chloroperoxidase, CPO)与Nafion分散的单壁碳纳米管分散液混合后直接滴涂到玻碳电极表面制得修饰电极. 这个固定了氯过氧化物酶的碳纳米管修饰玻碳电极, 在pH=5.0的磷酸缓冲溶液中测得的循环伏安曲线上有一对准可逆的氧化还原电流峰, 经过与裸电极和没有固定氯过氧化物酶的碳纳米管修饰电极上测得的循环伏安行为对比后确认, 碳纳米管对氯过氧化物酶与电极之间的电子传递反应具有很好的促进作用. 利用该修饰电极能催化一氯二甲酮氯化为二氯二甲酮, 无需添加过氧化氢作为反应启动剂, 紫外光谱的测试结果表明, 每摩尔氯过氧化物酶可催化氯化4.0×105 mol 的一氯二甲酮, 表现出很高的催化效率.     

新型手性亲核催化剂4-二甲胺基吡啶衍生物的研究进展

手性4-二甲胺基吡啶(DMAP, 4-Dimethylaminopyridine)衍生物作为具有较高催化活性和对映选择性的新型手性亲核催化剂, 已经在多种不对称催化反应中得到应用, 并取得了很好的研究成果. 目前, 手性DMAP衍生物化学的研究正成为催化不对称合成领域中一个十分活跃和引人注目的研究热点. 综述了手性DMAP衍生物化学近几年的研究进展.     

Position-dependent effective mass Schrödinger equations for PT-symmetric potentials

We use the method of point canonical transformations and choose the Rosen-Morse-type potential as the reference potential to study exact solutions of the position-dependent effective mass Schr?dinger equations. Choosing three position-dependent mass distributions, we construct seven exactly solvable target potentials with PT symmetry. The energy spectra of the bound states and corresponding wavefunctions for the PT-symmetric potentials are given in the exact closed forms. We also discuss the isospectrality of different Schr?dinger equations with the same mass distribution or different mass distributions for different PT-symmetric potentials.