BH+2与C2H2反应势能面的量子化学研究

用B3LYP/6-311G(d,p) 密度泛函方法和高级电子相关的CCSD(T)/6-311G(2df,p)偶合簇法研究BH+2与C2H2反应势能面. 结果表明 该势能面上存在(a) H2B+*C2H2, (b) HBCHCH2+, (c) H2BCCH+2和(d) H2*BHCCH+四种异构体, 其中(b)能量最低且在动力学上最稳定, (a), (c)和(d)在动力学上均不稳定; BH+2通过对C2H2的分步亲电加成以及随后的氢迁移和H2消除等反应形成离解产物HBCCH++H2, 该反应不需要活化能且大量放热. 计算结果有助于深入了解BH+2等缺电子硼氢正离子的反应行为.     

量热法研究氯化铒与甘氨酸配合物的标准生成焓

量热法测定;量热法研究氯化铒与甘氨酸配合物的标准生成焓     

A Novel Synthesis of Some Hexasubstituted Cyclotriphosphazenes

In recent years, many efforts were focused on the preparation and characterization of phosphazene which contained a framework of alternating phosphorous and nitrogen atoms with two substituent groups attached to each phosphorous atom1. It is noticeable that cyclophosphazene, especially hexaaryloxyphosphazene and perfluoroaryloxyphosphazene exhibit excellent thermal and chemical stability which can be used as fireproof materials, high temperature lubricants, vacuum pump oils and hard disk surfac…     

Direct Observation of Transition Metal Dichalcogenides in Liquid with Scanning Tunneling Microscopy

We present atomic-resolution images of TiSe\begin{document}$_2$\end{document}, MoTe\begin{document}$_2$\end{document} and TaS\begin{document}$_2$\end{document} single crystals in liquid condition using our home-built scanning tunneling microscopy (STM). By facilely cleaving of single crystals in liquid, we were able to keep the fresh surface not oxidized within a few hours. Using the high-stable home-built STM, we have obtained atomic resolution images of TiSe\begin{document}$_2$\end{document} accompanied with the single atom defects as well as the triangle defects in solution for the first time. Besides, the superstructure of MoTe\begin{document}$_2$\end{document} and hexagonal charge-density wave domain structure in nearly commensurate phase of TaS\begin{document}$_2$\end{document} were also obtained at room temperature (295 K). Our results provide a more efficient method in investigating the lively surface of transition metal dichalcogenides. Besides, the high stable liquid-phase STM will support the further investigations in liquid-phase catalysis or electrochemistry.     

季戊四醇四苯甲酰甲酸酯的合成及光引发性能

大分子光引发剂可以解决小分子光引发剂残留碎片带来的毒性对其在食品和医用材料领域应用的限制,为此,本文以苯甲酰甲酸(BF)和季戊四醇(PET)为原料,通过酰氯法在季戊四醇主链上引入了4个苯甲酰甲酸酯基团,制备了多官能度的季戊四醇四苯甲酰甲酸酯(PTF)大分子光引发剂。 PTF在225 ℃时失重15%,热稳定性优于2-羟基-2-甲基-1-苯基-1-丙酮(1173)光引发剂,与1173光引发剂相比,用PTF作光引发剂所制备的光固化涂料,在起始分解温度以及失去相同比例质量所需温度均提高了100 ℃以上。 PTF引发三羟甲基丙烷三丙烯酸酯(TMPTA)聚合时最大反应速率为0.037 s^-1,最终双键转化率为39.5%,PTF光引发活性大于1173光引发剂。 在同等实验条件下,PTF的相对小分子残留量仅为1173光引发剂的5%。     

Electrochemical Detection of Catechol on Boron‐doped Diamond Electrode Modified with Au/TiO2 Nanorod Composite

Au/TiO₂ nanorod composites with different ratios of [TiO₂]:[Au] have been prepared by chemically reducing AuCl₄^‐ on the positively charged TiO₂ nanorods surface and used to modify boron‐doped diamond (BDD) electrodes. The electrochemical behaviors of catechol on the bare and different Au/TiO₂ nanorod composites‐modified BDD electrodes are studied. The cyclic voltammetric results indicate that these different Au/TiO₂ nanorod composites‐modified BDD electrodes can enhance the electrocatalytic activity toward catechol detection, as compared with the bare BDD electrode. Among these different conditions, the Au/TiO₂‐BDD3 electrode (the ratio of [TiO₂]:[Au] is 27:1) is the most choice for catechol detection. The electrochemical response dependences of the Au/TiO₂‐BDD3 electrode on pH of solution and the applied potential are studied. The detection limit of catechol is found to be about 1.4 × 10^‐6 M in a linear range from 5 × 10^‐6 M to 200 × 10^‐6 M on the Au/TiO₂‐BDD3 electrode.     

原位氧化还原沉淀水热合成法制备LixMn2O4尖晶石

Li xMn2O4尖晶石是新一代的锂离子二次电池正极材料 [1], 其合成方法对材料的电化学性质影响很大[2].常规合成大多采用高温固相反应法, 此法具有反应温度高, 反应时间长, 容易产生缺陷和产物不纯净等缺点, 导致所合成的锂离子二次电池正极材料的性能较差. 目前用水热合成法制备电池正极材料Li xMn2O4尖晶石尚未见文献报道. 本文在常规水热合成法的基础上采用原位氧化还原沉淀水热合成法 [3]制备前驱物, 该法合成条件更温和, 而且使材料的综合性能得到了改善和提高.      

A μ3-OH- bridged two-dimensional zinc(Ⅱ) coordination polymer based on an anthryl ligand：Synthesis, characterization and luminescent properties

A two-dimensional (2D) 3,3,3,4,5,5,6-connected ZnⅡ coordination compound [Zn5(L)2(OH)6]∞ (L=9,10-dioxo-9,10-dihydroanthracene-1,8-dicarboxylate) has been synthesized and characterized by IR, elemental analysis, X-ray powder diffraction and single crystal X-ray diffraction analysis. Moreover, the luminescent properties of the ligand and corresponding compound have been briefly investigated.     

α-Cu_2Se精细结构的球差校正扫描透射电镜表征

目前学界对Cu_2Se低温α相的结构仍未认识清楚,而解决这一问题对理解Cu_2Se在相变过程中热电性能提升等特性具有重要意义。本文首次报道了由球差校正扫描透射电镜(STEM)拍摄到的沿■带轴的原子级分辨率高角环形暗场(HAADF)像,揭示了由Se原子以多种形式有序起伏产生的复杂结构。结合电子衍射图谱,分析了包含不同层数、通过相互组合构成α-Cu_2Se晶体的多种结构变体。使用QSTEM软件对构建的结构变体进行高分辨图像模拟,得到了与实验对应的HAADF像。该工作为更全面地理解α-Cu_2Se的结构提供了新的重要信息。