meso-四(对-磺酸基苯基)卟啉与痕量铋(Ⅲ)显色反应的研究

本文研究了在催化剂Hg(Ⅱ)存在下,meso-四(对-磺酸基苯基)卟啉与铋(Ⅲ)的显色反应。在室温下,在弱酸性介质中,反应在7min内完成。配合物的最大吸收波长为462nm,表观摩尔吸光系数为3.78×10~5L·mol~(-1)·cm~(-1)。Bi(Ⅲ)含量在0～10μg/mL范围内符合比尔定律。配合物的组成为Bi(Ⅲ):TPPS_4=2:3。是目前测定Bi(Ⅲ)灵敏度最高的显色反应之一。用于矿样中痕量铋(Ⅲ)的测定获得了较为满意的结果。     

均分散胶体的研究(Ⅳ)——钛酸锶均分散粒子的制备

烧制电子陶瓷用的SrTiO_3粉料不仅要求纯度高,而且对粒子的尺寸及均匀性也有严格要求。目前虽可用喷雾沉淀等方法制得尺寸为微米级的SrTiO_3粒子,但其形状与尺寸很不规整。用通常的均分散体系制备方法曾制得均分散BaTiO_3粒子,但由于制备溶液的浓度太低,难以实现工业化。其实,反应溶液浓度低、反应时间长、控制条件严格是大规模制备均分散粒子的共同弱点。本工作提出了一种简便、快速制备均分散SrTiO_3粒子的方法,有望实现均分散粒子制备的工业化。     

Investigation of the Crystallisation Behaviour of Lead Titanate (PT), Lead Zirconate (PZ) and Lead Zirconate Titanate (PZT) by EXAFS-Spectroscopy and X-Ray Diffraction

Two solid solutions of lead zirconium titanates PbZr _x Ti_{1 – x} O₃ (x = 0.1 and 0.35) as well as the reference compounds lead titanate and lead zirconate were prepared from zirconium and titanium n-propoxide, dissolved in 2-methoxyethanol, by sol-gel process. The amorphous products after pyrolysis of the dried gels and the crystalline phases were studied by EXAFS spectroscopy to monitor the structural changes from the amorphous oxide mixture to the crystalline ceramics after calcination. Additionally, the crystalline phases were identified by X-ray diffraction (XRD).It follows from the analysis of the EXAFS data that the local order of the amorphous phases seems to be completely different from that of the crystalline phase. There is no indication of a preformation of the local order of the perovskite structure. The analysis of our EXAFS spectra can be interpreted very consistently with the assumption that in the amorphous samples a segregation exists on molecular level and the low crystallisation temperatures are a consequence of very short diffusion paths.     

Study of the electronic and atomic structure of thermally treated SrTiO3(110) surfaces

The electronic structure of heated SrTiO₃(110) surfaces was investigated with metastable impact electron spectroscopy and ultraviolet photoelectron spectroscopy (He(I)). Scanning tunnelling microscopy and atomic force microscopy (AFM) were used to study the topology of the surface. The crystals were heated up to 1000°C under reducing conditions in ultrahigh vacuum or under oxidizing conditions in synthetic air for 1 h, respectively. Under both conditions microfacetting of the surface is observed. The experimental results are compared with ab initio Hartree–Fock calculations, also presented here, carried out for both ideal and reconstructed SrTiO₃(110) surfaces. The results give direct evidence for Ti termination of the faceted TiO₂ rows. Copyright © 2003 John Wiley & Sons, Ltd.     

焙烧处理下二氧化钛/钛酸盐纳米材料晶型和形貌的变化规律研究

通过调控酸碱浓度, 在水热条件下得到了金红石、锐钛矿、板钛矿、钛酸钠等一系列TiO₂/钛酸盐产物. 对上述TiO₂、酸洗处理后的钛酸盐等一系列不同晶型、不同形貌的样品进行焙烧处理, 系统性地研究焙烧温度的逐渐升高对产物晶型转变和形貌演化的规律性影响. 给出了水热酸碱浓度以及焙烧温度两个因素与TiO₂/钛酸盐纳米材料晶型和形貌变化行为关系的二维示意图. 依据奥斯特瓦尔德阶梯规则、经典热力学理论以及定向附着生长机理, 对TiO₂/钛酸产物的晶型晶体生长、晶型转变和形貌演化机理进行了探讨.     

结构稳定的CuO/TiO2纳米管的功能化溶胶修饰法制备及其催化CO氧化性能研究

以水热处理方法得到的钛酸纳米管为载体,采用含有醋酸铜的功能化钛溶胶对其进行一步浸渍修饰,制备结构稳定的CuO修饰TiO₂纳米管催化剂(CuO/TiO₂NTs)。通过XRD(X-射线衍射)、TEM(透射电子显微镜)、HR-TEM(高倍透射电子显微镜)、XPS(X-射线光电子能谱)、BET(氮气吸附-脱附法)、TPD(程序升温脱附法)等表征材料的结构和性质,并研究其催化CO氧化的性能。研究表明：经过溶胶浸渍处理过程,不仅将功能化铜组分负载在纳米管上,而且纳米管载体的耐热性能明显提高;催化剂载体、铜钛原子比及焙烧温度对催化剂的活性有明显影响,且400℃焙烧的Cu/Ti原子比为1∶5的CuO/TiO₂NTs的活性最高。     

Bismuth triflate catalyzed conjugate addition of indoles to α,β-enones

Reaction of indoles with electron deficient olefins under the influence of bismuth triflate has been studied at ambient temperature and affords the corresponding 3-alkylated indoles in excellent yields.     

Bi(OTf)3-catalyzed allylation of epoxides: a facile synthesis of homoallylic alcohols

Epoxides react smoothly with tetraallyltin in the presence of 2 mol% of Bi(OTf)₃ under mild reaction conditions to afford the corresponding homoallylic alcohols in excellent yields with high regioselectivity while aryl aziridines produce exclusively allyl amines in good yields under similar conditions.