Convenient procedure of Horner-Wadsworth-Emmons olefination for the synthesis of simple and functionalized α,β-unsaturated nitriles

A mild and practical procedure of Horner-Wadsworth-Emmons olefination promoted by lithium hydroxide and α-cyano phosphonates has been set up for the synthesis of α,β-unsaturated nitriles. The reaction conditions are tolerated by functionalized ketones and the exclusive formation of E-γ-hydroxy α,β-unsaturated nitriles has been observed.     

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.     

富锂正极材料Li[Li0.2Mn0.4Fe0.4]O2的表面包覆改性

用共沉淀法合成了富锂正极材料Li[Li0.2Mn0.4Fe0.4]O2,并对其表面进行Al2O3包覆。采用XRD、SEM和电化学测试等方法对样品进行表征。结果表明,与Li[Li0.2Mn0.4Fe0.4]O2相比,包覆改性后的Li[Li0.2Mn0.4Fe0.4]O2具有较好的电化学性能,其初始放电容量未明显降低,而循环寿命大大提高,4.0%Al2O3包覆处理的富锂正极材料经50次充放电循环后,容量衰减量在9%左右。     

Effect of Precursor Drying Process on the Properties of LiFePO4/C Composite with Low Carbon Content

<正>Properties of two LiFePO_4/C composites with low carbon content synthesized from precursors dried by spray drying and blast drying are investigated by scanning electron microscopy, X-ray diffraction, Raman spectroscopy and electrochemical measurements. The two samples have a different morphology and particle size, while the structure of LiFePO_4 is unaffected. The LiFePO_4/C composite prepared from the precursor dried by blast drying has a much lower surface resistance and a much better rate capability because the deposited carbon is more graphite-like and more conductive. The cycling performance is also much better for the LiFePO_4/C composite prepared from the precursor dried by blast drying because only a slight impedance growth is involved upon cycling. These results suggest that the precursor drying process has a significant impact on the properties of LiFePO_4/C composite, and its effect is highly dependent on the carbon content.     

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。     

卟啉敏化的钛酸盐纳米管的可见光催化活性

制备了四碘化5,10,15,20-四(对-N,N,N三甲基苯胺基)卟啉敏化的钛酸盐纳米管(TAPPI-TNTs),并利用甲基橙(MO)作为模型污染物考察了其可见光催化活性。结果表明,TAPPI-TNTs是一个高效的可见光催化剂,在其催化作用下,可见光照射1 h后,甲基橙的降解率为89%。与此相反,纯钛酸盐纳米管并不具有可见光催化活性。此外,TAPPI-TNTs的稳定性较高,可以多次循环使用,在第五次循环中,甲基橙的降解率仍可达到50%以上。这可能是由于带正电荷的卟啉与带负电荷的钛酸盐纳米管之间存在着较强的静电吸引作用,卟啉紧密地吸附在钛酸盐纳米管上,导致卟啉的光激发电子易于向钛酸盐纳米管转移,从而使钛酸盐纳米管得到了有效敏化。     

Deprotonative metalation of chloro- and bromopyridines using amido-based bimetallic species and regioselectivity-computed CH acidity relationships

A series of chloro- and bromopyridines have been deprotometalated by using a range of 2,2,6,6-tetramethylpiperidino-based mixed lithium-metal combinations. Whereas lithium-zinc and lithium-cadmium bases afforded different mono- and diiodides after subsequent interception with iodine, complete regioselectivities were observed with the corresponding lithium-copper combination, as demonstrated by subsequent trapping with benzoyl chlorides. The obtained selectivities have been discussed in light of the CH acidities of the substrates, determined both in the gas phase and as a solution in THF by using the DFT B3LYP method.     

The investigation of the (p,ρ,T) and (ps,ρs,Ts) properties of {(1−x)CH3OH + xLiBr} for the application in absorption refrigeration machines and heat pumps

The (p,ρ,T) and (p_s,ρ_s,T_s) properties of {(1−x)CH₃OH + xLiBr} over a wide range of state parameters are reported for the first time. The experiments were carried out in a constant volume piezometer over a temperature range from 298.15 K to 398.15 K, at 0.08421, 0.13617, 0.19692, 0.23133 and 0.26891 mole fractions and from atmospheric pressure up to 60 MPa. The experimental uncertainties are ΔT=±3 mK for temperature, Δp=±5·10⁻² MPa for high pressure and Δp=±5·10⁻⁴ MPa for atmospheric pressure, Δρ=±3·10⁻² kg · m⁻³ for density. An equation of state was derived for correlation of the experimental data of the solutions.