ClInPc-(TPD-PVK)光电导体性能的研究

本文以氯化酞菁铟(ClInPc)为载流子发生层(CGL),四苯基联苯胺(TPD)与聚乙烯咔唑(PVK)复合为载流子传输层(CTL),形成双层结构的功能分离型有机光电导体(P/R),研究了它的静电感光性能。结果表明,ClInPc/PMMA(30%)与TPD/PVK(1:1)两者匹配时的P/R具有良好的光电导性能,其电荷接受能力V_max≈800V,光电导率△V_t(ls)>70%,暗衰小(<50V/s),残余电位低(30V/s).由真空蒸镀成膜(CGL)所研制的P/R的光电导性能更为优异。     

孔雀石绿增感聚苯乙炔的光导体

采用电位放电技术研究孔雀石绿（ＭＧ）增感顺式聚苯乙炔（ｃｔ－ＰＰＡ）光导体的光敏性，发现孔雀石绿是顺式聚苯乙炔新的有效增感剂。以Ａｌ／ｃｔ－ＰＰＡ：ＭＧ：ＰＣ（１００：５：１０）（１～１．５μｍ）／ＰＶＫ：ＴＰＡ：ＰＣ（１０：１０：１）（１５～２０μｍ）构成的光导体显示好的光敏性：表面接受电位，Ｖｍａｘ＞７００Ｖ；残余电位，Ｖｍｉｎ＜５０Ｖ；暗衰速率，ＲＤ＜１０Ｖ／ｓ；光衰放电量，△Ｖｔ＞５０％（１．０ｓ）；半衰时间，Ｔ１２＝０．８７Ｓ；感光灵敏度，Ｓ＝２．３×１０－３（１ｘ．ｓ）－１，较未增感ＰＰＡ光导体有较大的提高。ＭＧ对ＰＰＡ为光谱增感     

甲醇对炭载铂和四羧基酞菁钴催化氧还原动力学的影响

运用旋转圆盘电极技术和线性扫描伏安方法研究比较了甲醇对炭载铂（Pt/C）和800 ℃热处理的炭载四羧基酞菁钴（CoPcTc/C）催化氧还原动力学的影响.结果表明，对于Pt/C催化剂，在大于0.64 V和小于0.18 V（vs SCE）的电位范围，甲醇的氧化和氧的还原互不影响，而在其它电位范围，甲醇使Pt/C催化氧还原的性能严重降低.对于800 ℃热处理的CoPcTc/C，在整个电位范围内，甲醇的存在对氧还原都没有影响，是一种活性较高、耐甲醇能力强的氧还原电催化剂.     

溴代酞菁铁配合物的光谱电化学性质研究

本文对μ-氧-四溴酞菁铁配合物([TBPcFe]₂O)的电化学性质及光谱电化学性质进行了研究。结果表明,μ-氧-四溴酞菁铁在所研究的电压区问内经历了三个单电子氧化还原反应,其半波电势为0.06V,—0.75V及—1.33V(相对于甘汞电极),分别对应于Fe³⁺/Fe³⁼、Fe²⁺/Fe⁺及TBPc^2-/TBPc^3-电对的氧化还原反应。光谱电化学性质研究亦观察到相应酞菁配合物的特征光谱。     

钒（V）—桑色素—溴化十六烷基三甲铵胶束增敏荧光光度法的研究和应用

研究了在pH2．5的HCI－NaAc介质中,溴化十六烷基三甲铵（CTMAB）对桑色素（morin)和钒（V）配合物荧光的增敏作用,建立了利用钒（V－morion-CTMAB胶束增敏荧光反应测定痕量钒的荧光光度新方法。方法的检出限为0．92μg/L,荧光强度与钒的含量在0．010－6．0μg/10mL范围内呈线性关系,配合物中钒（V）与桑色素的组成比为：V（V）：morin=1:1。方法可应用于天然水和食品中微量钒的测定。     

青蒿素及其衍生物电化学性质的研究I. 青蒿素在汞电极上的电化学还原

青蒿素及其衍生物代表着一类新型抗疟药。青蒿素分子中过氧基与抗疟活性密切相关。本文采用多种电化学方法研究了青蒿素分子中过氧基在Hg电极上的还原, 还原电位在0.0V(vs.Ag/AgCl)附近, 电极过程为不可逆还原, 反应电子数n=2, 半波电位E1/2=0.012V, 电子转移系数α=0.66, 表观标准电极反应速率常数ks'=6.34×10^-^6cm/s, 扩散系数D=4.3×10^-^6cm^2/s。反应产物在电极表面具有吸附性, 文中提出了可能的电化学反应机理。     

苯酚过氧化氢羟化过程中Dawson结构钼钒磷杂多化合物的ESR谱研究

研究了苯酚过氧化氢羟化过程中Dawson结构杂多化合物的ESR谱，通过对比不同反应时间后催化剂的波谱参数，分析了反应过程中V4+→V5+的变化情况．研究结果表明，在反应初期，催化剂仅存在少量V4+，在反应时间达到2h时V4+的含量迅速增多，并出现了V（Ⅰ）及V（Ⅱ）两种波谱参数相异的四价钒，其中V(Ⅰ)对应着V＝O键上的V4+，而V（Ⅱ）则对应着加氧中间物种，反应过程中V(Ⅱ)的含量迅速增多．两种钒均为羟化反应的活性中心     

温敏性金属酞菁聚合物的制备及光活性

对氨基锌酞菁进行改性,并将其以共价键接枝到聚N-异丙基丙烯酰胺分子链上,制得一种新型的既有温敏性又有光活性的锌酞菁聚合物．与小分子氨基锌酞菁相比,所合成的锌酞菁聚合物能溶解于大多数有机溶剂和水,而且,在水溶液中表现出良好的温敏性,其低临界溶解温度为34．1℃．通过锌酞菁聚合物对单线态氧捕捉剂1,3-二苯基苯并呋喃的光催化降解测试,结果表明在可见光照射下,锌酞菁聚合物无论在溶解状态还是沉淀状态都具有较高的光活性．基于这些特殊性能,这种锌酞菁温敏聚合物作为一种新型光敏剂,有望在光动力学治疗领域得到广泛的应用．     

取代苯醌在乙腈中的电化学和光谱电化学研究

研究了含有甲基、甲氧基、氟或氯等不同取代基的对苯醌衍生物在乙腈中的电化学和紫外-可见光谱电化学性质,并探讨了取代基对化合物电化学性质的影响.结果表明,每个化合物均可以发生两步可逆的单电子还原反应,分子中的供电子基能使还原反应电位发生负移,而吸电子基则可使电位发生正移.还原电位的变化值(ΔE)与取代基哈密特常数(∑σ)之间呈线性关系,其方程为:ΔE1=0.386 9∑σ-0.073 5(V),R2=0.996,ΔE2=0.280 3∑σ-0.114 5(V),R2=0.981.在控制电位还原时化合物的紫外可见光谱具有明显的变化,表明两步还原反应的产物分别为阴离子自由基(R)nQ.-和负二价阴离子(R)nQ2-(R=—CH3,—OCH3,—Cl,—F;n=0～4).     

二元ZnCo-LDH助催化剂对BiVO4光电化学性能的促进

钒酸铋(BiVO_4)是最有前景的将太阳能转化为氢能(STH)的光阳极材料之一,但其本身严重的电子-空穴复合严重影响了其实用性。本文中,我们报道了用一步电沉积法将高效的二元ZnCo-LDH助催化剂沉积在钒酸铋(BiVO_4)光阳极上,大大提升了钒酸铋(Bi VO4)的光吸收能力,并且加速了水氧化反应动力学,显著促进了光生空穴向半导体表面的转移,减轻了表面电荷复合。BiVO_4/ZnCo-LDH光阳极在1.23 V(vs RHE)偏压下,0.5 mol·L-1磷酸钾(KPi)电解液中的光电流密度达到2.85 mA·cm~(-2),是纯BiVO_4的2.59倍,且起始电位(Von)从930 m V下降到270 m V。BiVO_4/ZnCo-LDH复合光阳极表现出65%的高表面电荷分离效率(1.23 V(vs RHE)),而纯BiVO_4的仅为30%。     

有机电路及其基本元器件

半导体电路及其元器件是实现现代信息传递的重要组成部分,随着无机电路特别是硅基电路的研究发展进入瓶颈,有机电路及其基本元器件的研究对于电路及系统的未来发展意义更加重大。近十年来,有机电路及其基本元器件取得了飞速的发展,多种基本元件器性能已经达到可应用程度,特别是在显示领域,基于有机半导体制备的OLED显示电路已经成为新一代显示器的选择。同时,有机电路也因其所具有的低成本、可弯折、高透光等特性而具有了更多的发展空间。本综述从构成有机电路的各基本部件出发,以各部分器件在电路系统中的应用为线索,从系统信息采集、信息处理、信息存储和信息输出4个方面简述了各部分基础元件的发展情况,并以基于有机场效应晶体管的器件为基础,对器件的结构、电性能的优化以及所面临的问题进行了讨论。     

Recent progress in organic field-effect transistor-based integrated circuits

Organic integrated circuits are undergoing rapid development with the extensive research on organic semiconducting materials and the performance improvement of organic field-effect transistors. Organic integrated circuits not only cover all the major circuit types, their complexity, degree of integration, and performance have also been improved in recent years. In this review, recent advances in the design and fabrication of integrated circuits based on organic field-effect transistors are reported. The circuits are categorized into digital and analog, which are discussed in detail centering on the structure, fabrication process, and performance. In addition, progress in the modeling and simulation of organic integrated circuits are discussed as well, as they are key issues for the future development of organic electronics.     

The Synthesis and Optoelectronic Applications for Tellurophene-Based Small Molecules and Polymers

Tellurophene-based small molecules and polymers have received great attentions owing to their applications in thin-film transistors, solar cells, and sensors. This article reviews the current progress of the synthesis and applications of tellurophene-based small molecules and polymers. The physicochemical properties and optoelectronic applications of tellurophene-based materials are summarized and discussed. In the end, the challenges and outlook of tellurophene-based materials are presented.     

A Formal Rearrangement of Allylic Silanols

We show that 1M aqueous HCl/THF or NaBH₄/DMF allows for demercurative ring-opening of cyclic organomercurial synthons into secondary silanol products bearing terminal alkenes. We had previously demonstrated that primary allylic silanols are readily transformed into cyclic organomercurials using Hg(OTf)₂/NaHCO₃ in THF. Overall, this amounts to a facile two-step protocol for the rearrangement of primary allylic silanol substrates. Computational investigations suggest that this rearrangement is under thermodynamic control and that the di-tert-butylsilanol protecting group is essential for product selectivity.     

Low‐Threshold Non‐Doped Deep Blue Lasing from Monodisperse Truxene‐Cored Conjugated Starbursts with High Photostability

Herein, the photophysical, morphological, optical gain characteristics of a set of trigonal monodisperse starburst conjugated macromolecules ( Tr1‐Tr4 ) have been systematically investigated in order to elucidate the influence of the molecular structures on their optoelectronic performance. With increasing the oligofluorene arm length, absorption spectra were red‐shifted progressively, whereas an increase in photoluminescence quantum yields (PLQYs) and optical gain coefficients, and a corresponding reduction in amplified spontaneous emission (ASE) thresholds and loss coefficients were observed for Tr1‐Tr3 except for Tr4 . The results indicate that the effective conjugation length become saturated for Tr3 in this system. Impressively, the resulting molecules manifested very low ASE thresholds (4.4–11.6 μJ cm^?2) with high photostability, as well as high thermal stability. One dimensional distributed feedback (DFB) lasers exhibited a minimum lasing threshold of 10.38 nJ pulse^?1 (0.86 kW cm^?2, 4.325 μJ cm^?2) for Tr3 . It should be emphasized that the ASE threshold of Tr1‐Tr4 was nearly unchanged from room temperature to 200 °C. The results suggest that this kind of truxene‐cored conjugated starbursts with high photostability and low lasing thresholds are rather promising gain media for organic semiconductor lasers.     

功能性可拉伸有机电子器件的研究进展

可拉伸有机电子器件具有高机械稳定性、优异的电学稳定性、低成本和生物兼容性好等优点,是未来电子器件发展的重要方向.功能性可拉伸有机电子器件更是为可穿戴和可植入设备、智能医疗以及软体机器人等新兴高技术领域提供了新的研究思路.本文综述了近年来功能性可拉伸有机电子器件的研究进展,包括场效应、光电、存储以及传感等有机晶体管,发光二极管、交流电致发光、发光电化学电池等有机光电器件,太阳能电池、超级电容器、纳米发电机等有机能源存储与转换器件,压力、应变、触觉、温度、气体等有机传感器,忆阻器、磁存储、仿突触存储等有机存储器,以及其他集成电路系统元件,最后就功能性可拉伸有机电子器件存在的科学问题与未来的发展方向提出了建议.     

油酸包覆二茂铁有机磁体/金红石复合物的表征

制备了油酸包覆二茂铁有机磁体与天然矿物金红石（OPM/RC）复合物，用VSM强磁计，XRD、IR、XPS及SEM对包覆前后OPM/RC复合物的形态结构进行表征，结果表明，包覆复合物多以团聚体形式存在，两相间的界面存在一定程度以-C-O…Ti和-C-O…Fe化学键结合起来的六元环复合层，它有效地降低了复合物的电磁损耗，但在相同磁场下，其饱和磁化强度略下降，这可用油酸包覆复合物中OPM颗粒界面存在自旋钉扎效应进行解释。     

基于外场观测的大气二次有机气溶胶研究

二次有机气溶胶（SOA）是指挥发性有机物在大气中发生光化学氧化进入到颗粒相的产物,由于其具有强烈的环境效应、气候效应和人体健康效应,因此成为大气化学研究的热点. 然而由于SOA的复杂性和测量技术的限制,目前对SOA的研究还非常有限. 总体来说,对SOA的研究手段主要有三种方法：实验室模拟、模式模拟和基于外场观测的SOA研究. 由于SOA的研究非常广泛,本文仅综述了基于外场观测的SOA组成、来源和生成机制的研究,重点在于SOA组分的测量和总量的估算. 基于外场观测的SOA研究是随着技术的发展而发展的,早期的研究仅仅能对SOA的少数物种进行测量,主要是一些有机酸和多羟基化合物;也有利用一些假设对SOA进行粗略的估算,如受体模型法、非生物质燃烧水溶性有机物法;随着SOA实验室模拟研究和示踪物测量技术的发展,二次有机示踪物法真正做到了对特定前体物VOC生成SOA的估算;随着在线测量技术的提高,EC示踪/CO示踪和OC/EC比值法和基于气溶胶质谱（AMS）-正交矩阵模型（PMF）的方法被广泛应用于SOA的估算. 尤其是AMS-PMF联用方法的出现为SOA来源和生成机制的研究开拓了新的方向. 对AMS技术和示踪物技术的进一步联合和开发有望成为未来SOA研究重要的方向.     

First Preparations and Characterization of Conductive Polymer Crystalline Nanoneedles

Single crystalline nanoneedles of three families of the most studied conductive organic polymers - polythiophene, polyaniline and polypyrrole - were synthesized for the first time using an interfacial polymerization process that takes place with simultaneous crystallization. As the crystal growth is concurrent with polymerization, more ordered crystal packing can be expected. Most of the bulk conducting-polymer systems studied contains regions that are inhomogeneous. Single nanocrystals of conducting polymers have not been reported, although needle-shaped bulk crystals of the quarterphenyl cation radical salt have previously been studied. The investigation of processes in a nanodomain of a single crystal is critical in ascertaining the inherent electronic properties of polymer nanoelements. The organic conductive nanoneedles were characterized using TEM, HRTEM, electron diffraction, EDS, and EPR to establish their crystal structure and composition. Scanning tunneling microscopy/spectroscopy (STM/STS) investigation were conducted to examine their electronic behaviors, leading to the discovery of a field-induced conductance switching with response times on the millisecond level. The switch voltages are in the range of 3 to 4 volts in STM experiments, consistent with the trend of the band gap of the three polymers. The organic conductive nanoneedles with nano-tip having high density of mobile electron may serve as interesting elements for nanoscale electronics.