PTh / ZnO复合纳米粉的固相合成及其光谱特性

0引言导电聚合物/无机物纳米复合材料具有纳米材料和导电聚合物的共同特性,因此在电催化、二次充电电池材料、超级电容器材料等方面具有良好的应用前景[1]。聚噻吩(PTh)以及取代聚噻吩是导电聚合物领域中较早发现的具有环境稳定性和可加工性的材料之一。近年来,有关聚噻吩/无机物纳米复合材料的制备及其光电性能的研究倍受关注,Gebeyehu等[2]用PTh敏化纳米晶TiO2光伏电池,发现其光伏效率明显优于固态光伏电池;Jayant等[3]研究了PTh中的羧基基团的影响以及在纳米晶TiO2     

聚噻吩类导电聚合物及其复合膜修饰电极的制备及其在电分析化学中的应用

聚噻吩类导电聚合物修饰电极在电化学检测某些生物分子方面显示出独特的优势,尤其是聚(3-甲基噻吩)(P3MT)修饰电极,这是因为3-甲基噻吩易于电聚合成膜,得到的导电薄膜电导率高、电催化效果好、稳定性高、耐用、抗污染,而且还具有很好的选择性和灵敏性.     

聚3-(4-氟苯基)噻吩/碳化聚丙烯腈泡沫复合电极的电化学研究

噻吩衍生物是合成导电高分子材料的单体之一,在有机电致发光器件和电能存储等方面有着广泛的应用。聚3-(4-氟苯基)噻吩(PFPT)是一类既可进行p型掺杂又可进行n型掺杂的窄能带聚合物,在导电高分子型电化学电容器方面具有很好的应用前景,聚丙烯腈微孔膜已在锂离子电池方面有了很好的应用。若将它与碳纸复合后,再进行高温碳化和CO2活化,可制得导电性好、比表面积大的片状材料,作为电化学电容器的电极材料具有一定的双电层电容量．本文在三电极电解池中以这种材料的薄片为工作电极使3-(4-氟苯基)噻吩在乙腈溶液中进行电化学聚合,制备了聚3-(4-氟苯基)噻吩／碳化聚丙烯腈泡沫复合电极并研究了电极的电化学特性。     

聚丁基噻吩的合成及性能

用化学聚合方法合成了聚丁基噻吩导电材料,并研究了不同的聚合条件对聚合物性能的影响。聚丁基噻吩导电材料具有较好的稳定性和加工性,其掺杂态的导电率可达到10s/cm。     

导电聚合物超级电容器电极材料*

导电聚合物（聚苯胺,聚吡咯,聚噻吩）作为超级电容器电极材料的研究引起了人们广泛的兴趣,该类材料制备的超级电容器具有成本低、容量高、充放电时间短、环境友好和安全性高等优点。本文综述了近年来基于导电聚合物及其与无机材料（碳材料/金属氧化物材料）复合所得电极材料在超级电容器中的应用进展,指出具有纳米结构导电聚合物材料及导电聚合物与无机纳米材料的复合是超级电容器电极材料研究的重要发展方向。     

导电聚合物的现场电导/电化学研究——聚(3-甲基噻吩)和聚噻吩

本文提出一种研究导电聚合物的现场电位、电导测量/电化学方法。该实验方法基于一种可重复使用的玻璃碳-碳纤维组双电极。用该方法研究了聚(3-甲基噻吩)和聚噻吩的现场电位、电导/电化学行为。     

聚3-甲基噻吩的光电化学研究

利用光电化学方法研究了聚3-甲基噻吩的光电化学性质.其禁带宽度为1.93 eV.同时确定了它的价带、导带位置.研究还发现聚3-甲基噻吩属于直接跃迁半导体,具有很好的光电流稳定性.得到的最高IPCE值近1.0%.     

新型噻吩基取代卟啉的合成及其荧光光谱研究

卟啉由于其独特的光电性质以及在分子导线[1]、信息存储[2]、非线性光学材料[3,4]等方面的应用而受到关注.聚噻吩及其衍生物同样由于可作为电极材料和光学材料而被广泛研究[5].近几年来,人们广泛关注将卟啉和噻吩结合起来,并通过噻吩之间的偶连做成D-A-D型高分子,以便发现更独特的光学和电学性质[6,7].在本文中,我们报道了两种新型的中位噻吩基取代卟啉5,15-二(2-噻吩基)-2,8,12,18-四乙基-3,7,13,17-四甲基卟啉(7a)和5,15-二(2-联噻吩基)-2,8,12,18-四乙基-3,7,13,17-四甲基卟啉(7b)(61.2%)的合成(图1)及其光谱性质,其中荧光光谱的最大发射峰在631 am处,量子产率分别为4.1%(7a)和1.4%(7b).其聚合物的合成和性质见后文.     

可溶性聚3-[(二茂铁甲酸乙酯)三乙氧基]氧基噻吩的合成与性质表征

采用化学聚合方法合成了一种含二茂铁电活性基团的新型导电聚噻吩衍生物聚3-[(二茂铁甲酸乙酯)三乙氧基]氧基噻吩, 用1H NMR和红外光谱等方法对其结构进行了表征. 实验结果表明, 该聚合物可溶于三氯甲烷、四氢呋喃和丙酮等有机溶剂, 并且二茂铁在聚合物中依然保持良好的氧化还原活性, 对钠离子具有良好的选择性络合作用.     

导电聚合物电致变色材料*

由于在电致变色、显示、军事等领域的广泛应用,电致变色材料受到了人们越来越多的关注。本文综述了聚苯胺(PANI)类、聚噻吩(PTh)类、聚吡咯(PPy)类及复合导电聚合物电致变色材料的性能及其研究进展,同时简单地叙述了这些材料作为电致变色材料的应用前景,指出具有丰富颜色变化、良好的稳定性及成膜性的共聚物及有机/无机复合导电聚合物材料是未来电致变色材料发展的方向。     

Tetra-EDOT substituted 3D electrochromic polymers with lower band gaps

A couple of novel electrochromic materials poly(2,3,4,5-tetrakis(2,3-hydrothieno[3,4-b]dixin-5-yl)-1-methyl-1H-pyrrole)(P(t-EDOT-mPy))and poly(5,5',5",5'"-(thiophene-2,3,4,5-tetrayl)tetrakis(2,3-dihydrothieno[3,4-b][1,4]dioxine))(P(t-EDOTTh))are electrodeposited via multi-position polymerization of their tetra-EDOT substituted monomers t-EDOT-mPy and t-EDOT-Th,respectively.Compared with the linear 2D structured poly(thiophene)(E_g=2.2 eV)and poly(2,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophene)(E_g=1.7eV),P(t-EDOT-Th)(E_g=1.62eV)has the lowest band gap.Hence,we speculate that the band gaps of the two polymers,having 3D structures,are decreased in contrast to non-substituted polymers or bi-EDOT substituted polymers,thiophene and 1-methyl-1H-pyrrole.The results indicated that P(t-EDOT-Th)thin films are more stable and show higher transmittance amid two polymers,which may find their utilization in organic optoelectronics.     

Small band gap conjugated polymers based on thiophene–thienopyrazine copolymers

In this study, five small band gap thiophene ( TH )–thienopyrazine ( TP ) conjugated copolymers were synthesized by Stille‐coupling reaction. The polymer structures consisted of one to four thiophene rings with the TP of different side groups provided a systematical investigation on the structure–electronic property relationship. The absorption maxima of the polymer films decreased from 850 to 590 nm as the thiophene moieties increased from thiophene to quaterthiophene. The optical and electrochemical band gaps of the studied poly[2,3‐didodecyl‐5‐(thiophen‐2‐yl)thieno[3,4‐b]pyrazine] ( PTHTP‐C12 ) were 0.97 and 0.78 eV, respectively, indicating a significant intramolecular charge transfer. The theoretical geometry and electronic properties of the TH ‐ TP copolymers by the density functional theory at the B3LYP level and 6‐31G(d) basis set suggested that the bond length alternation enlarged with enhancing the thiophene content and resulted in the variation on the polymer band gap. The relatively small theoretical effective mass of poly( TH ‐alt‐ TP ) also indicated its potential applications for field transistor applications. Our study demonstrates the tunable electronic properties of small band gap copolymers by the thiophene content and the resulted geometry variation. Such polymers could be potentially used for near‐infrared electronic and optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5872–5883, 2007     

Regioselective grignard metathesis reaction of 2,5‐dibromo‐3‐(6′‐hexylpyridine‐2′‐yl)thiophene and kumada coupling polymerization

2,5‐Dibromo‐3‐(6′‐hexylpyridine‐2′‐yl)thiophene ( DBPyTh ) was synthesized by the Suzuki coupling reaction between two aromatic compounds followed by the bromination. The Grignard metathesis reaction of DBPyTh with isopropylmagnesium chloride proceeded in 85% conversion and the regioselective halogen–metal exchange at the 2‐position was confirmed. Namely, 5‐bromo‐2‐chloromagnesio‐3‐(6′‐hexylpyridine‐2′‐yl)thiophene and 2‐bromo‐5‐chloromagnesio‐3‐(6′‐hexylpyridine‐2′‐yl)thiophene were generated in 90:10 molar ratio. Subsequently, the Kumada coupling polymerization was carried out using 1,3‐bis(diphenylphosphinopropane)nickel(II) dichloride to obtain poly(3‐(6′‐hexylpyridine‐2′‐yl)thiophene) ( PolyPyTh ). The polymer molecular weight could be roughly controlled by the catalyst concentration and the molecular weight distribution ranged from 1.25 to 1.80. The gas chromatograph analysis indicated that 5‐bromo‐2‐chloromagnesio‐3‐(6′‐hexylpyridine‐2′‐yl)thiophene was preferentially polymerized in 90% conversion and the percentage of the head‐to‐tail content (regioregularity) was calculated to be 96%. The matrix‐assisted laser desorption/ionization time‐of‐fright mass spectrum indicated that both polymer chain ends were substituted with the hydrogen atom. The absorption maxima of polymer in CHCl₃ and thin film were observed at 447 and 457 nm, respectively, which were blue‐shifted compared with poly(3‐(4′‐octylphenyl)thiophene). From the CV measurement of the polymer thin film, highest occupied molecular orbital (HOMO) (?5.31 eV) and lowest unoccupied molecular orbital (LUMO) (?3.76 eV) energy levels were calculated from the oxidation and reduction onset potentials, respectively, and the electrochemical band gap energy was determined to be 1.62 eV. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

纳米结构TiO2/聚3-甲基噻吩多孔膜电极光电化学研究

用光电流作用谱、光电流-电势图、紫外-可见吸收光谱等光电化学方法研究了导电玻璃(ITO)/TiO₂/聚3-甲基噻吩(PMT)电极的光电转换性质. 结果表明, PMT膜为p型半导体, 其禁带宽度为1.93 eV. 并通过循环伏安和光电化学方法确定了其导带位置为－3.44 eV, 价带为－5.37 eV, 在纳米TiO₂与PMT之间存在p-n异质结, ITO/TiO₂/PMT电极不仅提高了光电流, 而且使产生光电流的起始波长红移至＞600 nm, 从而提高了宽禁带半导体的光电转换效率.     

Poly(pyrazinoquinoxaline)s: New n‐Type Conjugated Polymers That Exhibit Highly Reversible Reduction and High Electron Affinity

Summary: The pyrazinoquinoxaline‐based conjugated polymers poly(2,7‐diphenylpyrazino(2,3‐g)quinoxaline‐3,8‐diyl‐1,4‐phenylene) (PZQP) and poly(2,7‐diphenylpyrazino(2,3‐g)quinoxaline‐3,8‐diyl‐2,5‐thiophene) (PZQT) have been synthesized and characterized. PZQP and PZQT have optical band gaps of 2.44 and 1.76 eV, respectively. Both polymers showed highly reversible electrochemical reduction, with an electron affinity of 3.6 eV for PZQP and 3.8 eV for PZQT. The electronic structures of PZQP, PZQT, and related poly(pyrazinoquinoxaline)s, were calculated by density functional theory and compared with the experimental results.

Molecular structure and reduction cyclic voltammogram of PZQP.     

纳米结构TiO2/聚3-己基噻吩多孔膜电极光电性能研究

用光电流作用谱、光电流-电势图等光电化学方法研究了ITO/聚3-己基噻吩(ITO/ P3HT)膜和纳米结构TiO2/聚3-己基噻吩(TiO2/P3HT)复合膜的光电转换性质. 结果表明, P3HT膜的禁带宽度为1.89 eV, 价带位置为－5.4 eV. 在ITO/TiO2/ P3HT复合膜电极中存在p-n异质结, 在一定条件下异质结的存在有利于光生电子-空穴对的分离. P3HT修饰ITO/TiO2电极可使光电流发生明显的红移, 从而提高了宽禁带半导体的光电转换效率.     

Regioregular copolymers of 3-alkoxythiophene and their photovoltaic application

Low band gap conjugated polymers with proper energy levels for charge transfer are required to achieve high-efficiency polymer solar cells. We report the synthesis and characterization of two new regioregular copolymers that are based on 3-alkoxythiophene monomers: poly(3-octylthiophene-2,5-diyl-co-3-decyloxythiophene-2,5-diyl) (POT-co-DOT) and poly{(9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-decyloxythien-2-yl)-2,1,3-benzothiadiazole]-5',5' '-diyl} (PF-co-DTB). Compared to the alkyl substituents, the alkoxy side chains on the thiophene units can effectively lower the band gap of copolymers and enhance the charge transfer to electron acceptors such as (6,6)-phenyl C(61)-butyric acid methyl ester (PCBM). The chemical structure and regioregularity of the copolymers were confirmed by NMR. Both copolymers are readily soluble in organic solvents and form high-quality thin films. Electrochemical and photophysical studies reveal band gaps of 1.64 eV for POT-co-DOT and 1.78 eV for PF-co-DTB. Bulk heterojunction photovoltaic devices were fabricated using blends of these copolymers with PCBM as the active layer, ITO-glass as the anode, and aluminum as the cathode. Power conversion efficiency of 1.6% was obtained under simulated solar light AM 1.5 G (100 mW/cm(2)) from a solar cell with an active layer containing 20 wt % PF-co-DTB and 80 wt % PCBM. Regioregular poly(3-decyloxythiophene-2,5-diyl) (P3DOT) was also studied for comparison purposes.     

烷基和烷氧基取代聚噻吩的合成、表征与光电性能

Fe(Ⅲ )氧化催化法合成了 4种聚噻吩衍生物 ,3 十二烷基聚噻吩 (Pat12 ) ,3 辛氧基聚噻吩 (Paot8) ,3,4 二 (十二烷基 )聚噻吩 (Pat12 12 )和 3 (十二烷基 )噻吩 3 (辛氧基 )噻吩共聚物 (CoPt12 o8) .发现这些衍生物易溶于多种常用有机溶剂 .用GPC法测定了各聚合物分子量 ,用1 H NMR法表征了各聚合物化学结构 .对比研究了这些聚合物紫外 可见吸收性能 ,光致发光性能和能隙 .对其电致发光性能进行测定的结果 ,得到了Pat12 ,Pat12 12和Paot8的电致发光光谱 .发射峰分别为 6 70nm ,5 6 0nm和 6 4 0nm .发光颜色分别为红色 ,黄色和红橙色 .聚合物的光电性能与主链电子结构有密切关系 .探讨了取代基种类和数量对聚合物能带结构 ,光电性能的影响 .     

Poly(thieno[3,4-b]thiophene)-poly(styrene sulfonate): a low band gap, water dispersible conjugated polymer

Herein we report the oxidative chemical polymerization of thieno[3,4-b]thiophene (T34bT) using several different oxidants including ferric sulfate, ammonium persulfate, and hydrogen peroxide in the presence of poly(styrenesulfonic acid) in water and properties of the resulting poly(thieno[3,4-b]thiophene)-poly(styrenesulfonic acid) (PT34bT-PSS) dispersion. The PT34bT-PSS is rendered a colloidal dispersion in water with a particle size diameter ranging between 180 and 220 nm depending on the oxidant used for polymerization. PT34bT-PSS films have band gaps of ca. 1 eV (1260 nm) as determined by the onset of the pi to pi transition from the vis-NIR spectrum with absorption maxima ranging from 1.4 eV (912 nm) to 1.7 eV (724 nm). The neutral and oxidized forms of PT34bT-PSS prepared from ferric sulfate dispersed in water were blue and lime green, respectively, whereas the neutral and oxidized forms of PT34bT-PSS prepared from ammonium persulfate and hydrogen peroxide were blue and blue-green, respectively. Spectral properties of the PT34bT-PSS dispersion can be tuned by the combination of oxidants. PT34bT-PSS films showed ca. 100% cation dominant ion transport behavior as determined by electrochemical gravimetry with each charge-discharge cycle and the doping level of the polymer was calculated to be 26%. Electrical conductivities for these polymers were found to be dependent on chemical oxidants used and varied from 10(-2) to 10(-4) S/cm.