Fine-tuning the molecular energy levels by incorporating thiophene units onto the π-backbone of core-expanded naphthalene diimides

A series of core-expanded naphthalene diimides (NDI-DTYM) and thiophene-based derivatives (1a-c) were designed and synthesized to investigate the relationship between molecular structures and the highest occupied molecular orbital (HOMO) energy levels but has little impact on the lowest unoccupied molecular orbital (LUMO) energy levels. The results demonstrated that increasing the number of thiophene units can gradually elevate the HOMO energy levels but had little impact on the LUMO energy levels. The n-channel organic field-effect transistors (OFETs) based on 1b and 1c have demonstrated that these almost unchanged LUMO energy levels are proper to transport electrons.     

用于监控电镀槽液的CVS技术

介绍CVS应用技术。CVS是目前半导体以及电路板业界最受广泛采用,监控电镀液中有机添加剂的技术。CVS精确分析所得的结果,可以用来作为离线或在线添加有机添加剂的依据,以保障槽液的品质。本文详细讨论CVS技术的电化学原理,并提供应用实例以作进一步解说。     

有机杀虫剂荧光光谱检测实验研究

研究了氨基甲酸酯类、苯甲酰脲类、杀菌剂类等几种常用有机杀虫剂的荧光特征,为进一步利用荧光法检测农药提供了理论依据。结果表明, 这些有机杀虫剂在一定的溶剂条件下受紫外光激发时能够 发出很强的荧光,而且荧光光谱清晰、分辨率高,证明利用荧光光谱法对相关杀虫剂进行定性定量检测分析是可行的。     

介孔分子筛Al-MCM-41的合成与催化异构化性能

采用正硅酸乙酯(TEOS)为硅源,九水硝酸铝为铝源,十六烷基三甲基溴化胺(CTMABr)为模板剂,在室温条件下合成了介孔Al-MCM-41分子筛.通过XRD、N2等温吸附、SEM、FTIR等分析测试手段表征了分子筛的介孔结构和表面性质.结果表明所合成的分子筛有良好的介孔结构和较高的有序度,并且有较高的比表面积(达到816 m2·g-1)和窄的孔径分布.采用程序升温的焙烧方式、凝胶Al/Si比最大范围控制在0.06～0.13有利于合成高度有序的介孔Al-MCM-41分子筛.评价结果表明,所合成的Al-MCM-41分子筛对桥式四氢双环戊二烯(endo-TCD)异构化反应合成挂式异构体exo-TCD及金刚烷具有较高的催化活性和极高的选择性.     

Enhanced sonocatalytic degradation of organic dyes from aqueous solutions by novel synthesis of mesoporous Fe3O4-graphene/ZnO@SiO2 nanocomposites

Fe₃O₄-graphene/ZnO@mesoporous-SiO₂ (MGZ@SiO₂) nanocomposites was synthesized via a simple one pot hydrothermal method. The as-obtained samples were investigated using various techniques, as follows: scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and specific surface area (BET) vibrating sample magnetometer (VSM), among others. The sonocatalytic activities of the catalysts were tested according to the oxidation for the removal of methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) under ultrasonic irradiation. The optimal conditions including the irradiation time, pH, dye concentration, catalyst dosage, and ultrasonic intensity are 60 min, 11, 50 mg/L, 1.00 g/L, and 40 W/m², respectively. The MGZ@SiO₂ showed the higher enhanced sonocatalytic degradation from among the three dyes; furthermore, the sonocatalytic-degradation mechanism is discussed. This study shows that the MGZ@SiO₂ can be applied as a novel-design catalyst for the removal of organic pollutants from aqueous solutions.     

Direct current and impedance spectroscopic studies on MoO3 modified ZnPc/ITO Schottky diodes

We use experimental results of direct current and low signal impedance spectroscopy to investigate the conduction mechanism in organic semiconductor ZnPc. The experimental results demonstrate an increase in current and holes mobility by the introduction of a thin MoO₃ film at the ITO/ZnPc interface. This significantly improves the device performance. The improvement is explained in terms of the reduction in the effective barrier for charge transfer from ZnPc to ITO.     

某些含氮有机物光催化氧化产生的自由基中间体

本文用自旋捕捉技术与ESR相结合的方法研究了某些含氮有机物TiO₂光催化降解的过程中形成的活泼中间体.选择的化合物中有丁胺、戊胺、庚胺、六氢吡啶、吡啶、2-甲基吡啶、2,6-二甲基吡啶,这些分子中的氮原子分别作为初级脂肪胺、饱和环中的二级胺以及芳环中的三级胺出现,实验中观察到N-中心自由基及C-中心自由基与自旋捕捉剂加合物的ESR信号,表明这些自由基参与这些化合物光降解的初始过程,对深入了解其光降机理是有意义的.     

Electron phonon interactions and superconductivity in α ′ -TTF[Pd(dmit)2]2

A simple model is developed to understand superconductivity in α ^′ -TTF[Pd(dmit)₂]₂. We include electron-intra molecular and intermolecular phonon interactions as the mechanism of superconductivity. Intramolecular vibrations included are the eight symmetric A_g modes of the Pd(dmit)₂ molecule. Intermolecular vibrations included are the longitudinal acoustic and transverse acoustic (LA and TA) modes of the Pd(dmit)₂ column. All the electron-phonon coupling constants are calculated from first principles. We find that largest el-intramolecular vibration coupling is to the A_g mode with the highest frequency (1449 cm^-1). The el-intermolecular coupling to the LA mode is found to be larger than the total el-intramolecular couplings. We also find el-(TA)phonon coupling to be at least an order of magnitude smaller than el-(LA)phonon coupling. Estimate of superconducting transition temperature is comparable to experimental result. We also provide a detailed discussion, employing the results of recent numerical calculations on two-chain Hubbard model and the specific material parameters, on the relative importance of el-ph and Coulomb-origin mechanisms of superconductivity in α ^′ -TTF[Pd(dmit)₂]₂ and TTF[Ni(dmit) ₂ ] ₂ . Received 29 March 2001 and Received in final form 7 August 2001     

几种稠环芳烃有机EL材料性能的量子化学理论研究

采用量子化学半经验方法（ＲＨＦ／ＰＭ３）对几种稠环芳烃化合物电致发光（ＥＬ）材料的性质进行了理论研究。利用能量梯度法优化构型,对各优化的构型作振动分析,均未出现虚频率。在此基础上,采用ＲＨＦ／ＣＩＳ方法计算其电子光谱。并给出了化合物ＥＬ１,ＥＬ２电子光谱的最大波长λ与ＣＩＳ组态之间的关系。所有计算结果与实验值基本吻合。     

Magnetic anisotropy and low-frequency dielectric response of weak ferromagnetic phase in κ-(BEDT-TTF)2Cu[N(CN)2]Cl, where BEDT-TTF is Bis(ethylenedithio)tetrathiafulvalene

We report a detailed characterization of the magnetism and AC transport in single crystals of the organic conductor -(BEDT-TTF)₂Cu[N(CN)₂]Cl by means of magnetic anisotropy measurements and low-frequency dielectric spectroscopy. Magnetic anisotropy obeys Curie-Weiss law with negative Curie-Weiss temperature in the temperature range 300 K-70 K. An antiferromagnetic transition with concomitant canted antiferromagnetic state is established at 22 K. A large hysteresis in the spin-flop transition and magnetic field reversal of the weak ferromagnetic magnetization are documented for the first time. A broad dielectric relaxation mode of moderate strength () emerges at 32 K, and weakens with temperature. The mean relaxation time, much larger than that expected for single-particle excitations, is thermally activated in a manner similar to the DC conductivity and saturates below 22 K. These features suggest the origin of the broad relaxation as an intrinsic property of the weak ferromagnetic ground state. We propose a charged domain wall in a random ferromagnetic domain structure as the relaxation entity. We argue that the observed features might be well described if Dzyaloshinsky-Moriya interaction is taken into account. A Debye relaxation with similar temperature dependence was also observed and seems to be related to an additional ferromagnetic-like, most probably, field-induced phase. We tentatively associate this phase, whose tiny contribution was sample dependent, with a Cu²⁺ magnetic subsystem. Received 15 June 1998 and Received in final form 1 February 1999