导电高分子聚噻吩衍生物的研究进展

聚噻吩是研究最为广泛的功能高分子材料。介绍了烷基取代、带支链和杂原子取代的各类聚噻吩衍生物的结构和合成方法 ,以及其作为新型的导电高分子材料的电光学性能和应用研究     

导电聚合物的合成与应用

本文简要的介绍了导电高分子的发现、分类和导电机理,并选取其中应用广泛的三种聚合物:聚噻吩、聚吡咯和聚苯胺作详细介绍,并介绍了这三种聚合物的主要合成方法及一些主要的应用,最后展望高分子的未来。     

手性导电高分子聚合物的研究进展

手性导电高分子聚合物在手性高分子领域里有很多独特的化学性质,已成为功能材料领域的研究热点。综述了聚苯胺、聚吡咯和聚噻吩等一些经典手性导电高分子聚合物的合成途径:当共轭的导电聚合物链上带有对映体纯取代基或有手性的掺杂阴离子时,其光学活性可以被π-π*电子吸收带所诱导;阐述了它们的合成发展史、现状、显著特性及手性导电高聚合物的应用前景。     

一些导电高分子研究的新进展

综述了近年来国际上导电高分子,尤其是可溶性导电高分子的研究进展。介绍了聚噻吩、聚吡咯、聚苯胺等几类热门研究的导电高分子的发展状况。     

两种聚噻吩类新型电致发光材料的合成与性能

报道了以无水FeCl3为催化剂合成异戊基取代和戊氧基取代聚噻吩的实验过程,两种聚合物稀溶液和薄膜的光发射、光吸收性能和用这两种材料作发光层制作的发光二极管的光电性能的初步研究结果.两种聚合物均具有较高的纯度和分子量.两种材料均显示了较好的发光性能,其电致发光颜色均为红橙色.烷氧基取代聚噻吩均聚物电致发光性能在学术界尚属首次发现.     

聚噻吩类衍生物电致发光材料研究进展

介绍了典型的具有光电性能的噻吩类导电高分子,包括烷基取代、侧链含杂原子取代以及与其他单体共聚的聚噻吩衍生物近年来的研究进展,对它们的制备、结构及发光性能进行了归纳、总结和评论,并对其今后的发展前景进行了展望。     

溶液混合与界面渗透法制备聚噻吩衍生物/聚酰亚胺导电复合材料的研究

本文介绍了高分子溶液混合与界面渗透法制备导电高分子复合材料的方法并对复合材料的结构和性能进行了表征.十二烷基取代聚噻吩四氢呋喃溶液与聚酰亚胺酸N-甲基吡咯烷酮在一定时间界面的互相渗透,十二烷基取代聚噻吩可嵌入聚酰亚胺酸层中.在溶剂挥发后,用化学或加热的方法进行酰胺化而得到稳定的导电高分子复合膜.表面电阻率、热失重及扫描电镜分析表明,与溶液混合法相比,界面渗透法制备的复合材料具有良好导电性能和稳定性.     

聚噻吩乙炔的合成及其导电性

对在水和甲醇－水混合介质中合成的聚噻吩乙炔（ＰＴＶ）前聚物（ｐｒｅｃｕｒｓｏｒ ｐｏｌｙｍｅｒ）的结构和性能进行了研究。不同聚合介质条件对单体转化率及前聚物的产率有一定影响。不同取代侧基影响ＰＴＶ前聚物的溶解性和热处理性能。并对ＰＴＶ膜碘掺杂后的导电率进行了初步研究。     

聚噻吩及其衍生物基复合材料研究进展

聚噻吩因其良好的溶解性、高电导率和环境稳定性成为导电高分子研究的热门领域之一。综述了聚噻吩及其衍生物基复合材料的研究进展及其制备方法(原位聚合法、电化学法、插层法、界面聚合法、乳液法和共混法等),介绍了聚噻吩类复合材料在电容器、电致变色和电磁方面的应用前景及现状,指出了聚噻吩及其衍生物基复合材料研究中普遍存在的易脱掺杂、电导率不高和性能不稳定等问题。     

π-共轭导电高分子材料的研究进展及存在问题

对新型共轭导电高分子材料的导电机理进行了分析，综合评述了聚对苯（ＰＰＰ）、聚吡咯（ＰＰＹ）、聚噻吩（ＰＴＨ）、聚苯胺（ＰＡｎ）和聚苯基乙炔（ＰＰＶ）的最新制备方法，并指出了共轭导电高分子目前存在问题及发展方向。     

Synthesis,characterization and comparison of polythiophene–carbon nanocomposite materials as Pt electrocatalyst supports for fuel cell applications

A novel polymer–carbon (PTh–C) nanocomposites containing different percentages of polythiophene (10, 20 and 50% (w/w)) and carbon (Vulcan XC-72) was prepared by a facile solution dispersion method and used to support platinum nanoparticles. The effect of using different percentages of polythiophene in nanocomposites and subsequently prepared electrocatalysts was investigated. The resultant electrocatalysts were extensively characterized by physical (X-ray diffraction (XRD) and transmission electron microscopy (TEM)) and electrochemical (cyclic voltammetry (CV)) techniques. The TEM results showed that the fine Pt nanoparticles prepared by ethylene glycol (EG) method were distributed on the surface of the 50% PTh–C nanocomposites successfully. From the XRD patterns, the average size of dispersed Pt nanoparticles with the face-centered cubic (fcc) structure on 50% PTh–C, 20% PTh–C, 10% PTh–C and carbon were about 4.9, 5.2, 5.4 and 6.1 nm, respectively. The conductivity of PTh–C with different percentages of pure PTh was compared with the conductivity of the corresponding support of pure PTh. It is observed that the conductivity of 50% PTh–C nanocomposites is about 600 times higher than that of pure PTh. Finally, CV measurements of hydrogen and methanol oxidations indicated that Pt/50% PTh–C had a higher electrochemical surface area and higher catalytic activity for methanol oxidation reaction compared to other electrocatalysts. These measurements showed that the Pt/50% PTh–C electrocatalyst by the value of 3.85 had higher \(I_{\mathrm{f}}/I_{\mathrm{b}}\) ratio with respect to Pt/10% PTh–C and Pt/20% PTh–C by the values of 2.66 and 2.0, respectively.     

Self-assembled Ti3C2Tx-MXene/PTh composite electrodes for electrochemical capacitors

Recently, MXene are being extensively utilized as an electrode material for electrochemical capacitors owing to its excellent electrochemical performance. Furthermore, its excellent properties are enhanced by compounding it with other materials as the electrode material of electrochemical capacitor. In this study, MXene has been obtained by selective etching, Polythiophene (PTh) was prepared by chemical oxidative polymerization, and MXene/PTh composites with different mass ratios have been synthesized by the vacuum filtration self-assembly method. MXene nanosheets have the comprehensive function of combining PTh nanoparticles, and acting as flexible substrates. PTh nanoparticles can provide high pseudo-capacitance and inhibit the stacking of MXene, thus achieving a good synergistic effect. The results demonstrate that the M/PTh-3 composite has the best capacitance with a maximum value of 265.96 F g^?1. The specific capacitance remains at 91.5% even after 500 cycles, which demonstrates that the composite electrode is a promising material for the high-performance electrochemical capacitor applications.

     

聚噻吩/纳米MnO2复合材料的制备表征及电化学性能

纳米二氧化锰（MnO₂）作为超级电容材料已被广泛研究。为了改善其充放电性能,采用原位化学氧化聚合法制备聚噻吩/纳米MnO₂ （PTh/MnO₂）复合材料,对纳米MnO₂进行性能改性。通过改变聚噻吩在PTh/MnO₂复合材料中的掺杂量,制备出一系列的复合材料。采用傅里叶转换红外光谱（FIIR）、X射线衍射仪（XRD）、场发射扫描电子显微镜（FE-SEM）和透射电子显微镜（TEM）对PTh/MnO₂复合材料的化学性能、晶体结构以及表面形貌等进行了详细考察。接着采用CT001A型电池测试系统对以PTh/MnO₂复合材料做负极所制得的密封扣式电池进行了充放电性能测试。结果表明,MnO₂和聚噻吩在不同的PTh/MnO₂复合材料中形貌各异。当聚噻吩含量为8wt%~10wt%时,MnO₂在PTh/MnO₂复合材料中分布最为均匀;当聚噻吩含量较高时,MnO₂的形貌受到严重影响,其原来的管状结构接近消失。聚噻吩含量的不同,同样也影响了电池的充放电性能。当聚噻吩的含量为20wt%时,在循环20次后,电池的平衡容量为最高,可达700 mAh/g。这明显高于以纳米MnO₂为负极时的电池容量。由此可见,聚噻吩对纳米MnO₂的充放电性能具有明显的增强作用。该研究为PTh/MnO₂复合材料作为电池负极材料的使用提供了实验基础。     

Synthesis, characterization, electrical and thermal properties of nanocomposite of polythiophene with nanophotoadduct: a potent composite for electronic use

Materials having high thermal stability and electrical conductivity form potential candidates for electronics. In this study, a thermally stable nanocomposite of nanophotoadduct of pentaamminechlorocobalt(III) chloride with hexamine and polythiophene (PTh) was prepared by oxidative chemical polymerization in the presence of FeCl₃ as oxidant and thiophene monomer. Photoadduct was obtained by photoirradiation followed by substitution with hexamine ligand which was then milled in G5 planetary ball mill to obtain nanophotoadduct which is confirmed by X-ray powder diffraction. The formation of nanophotoadduct and its incorporation in PTh structure was endorsed by fourier transform infrared analysis. Empirical formula of the nanophotoadduct was found to be [Co(NH₃)₂(OH)₃C₆H₁₂N₄]·2H₂O. SEM analysis revealed uniform distribution of nanophotoadduct in PTh matrix. Crystallite size and strain analysis revealed further decrease in size from 34 (nanophotoadduct) to 15 nm (nanocomposite) using different methods of analysis which were well correlated. This size reduction was attributed to the microstrain in the nanocomposite. TG revealed that the nanocomposite and PTh underwent 62 and 80 % weight loss at 1,000 °C respectively which clearly indicated the higher thermal stability of nanocomposite compared to pure PTh. Little change in the glass transition temperatures of PTh (170 °C) and nanocomposite (167 °C) is observed from DSC which indicated smaller plasticizing effect of nanophotoadduct. I–V curves of nanophotoadduct showed its diode like behavior while as nanocomposite depict nearly ohmic behavior. These results illustrate that the nanophotoadduct play two important roles, one that it acts as a Schottky diode material and second that it increases the conductance and thermal stability of PTh. Nanocomposite thus obtained can operate at relatively high temperatures in electrical appliances.     

Highly conductive polymer materials based multi-walled carbon nanotubes as counter electrodes for dye-sensitized solar cells

Poly(3,4-ethylenedioxxythiophene) (PEDOT), polyaniline (PANI) and polythiophene (PTh) based multi-walled carbon nanotube (MWCNT) composites were successfully prepared using RF-rotating plasma grafting method. Morphological characterizations of composites were determined using scanning electron microscopy (SEM), which showed that conducting polymers (CPs) of PEDOT, PANI and PTh were coated on the surface of CNTs. The surface properties of the Carbon Nanotube (CNT) composites were also determined by using Infrared Spectra (FT-IR), X-ray Photon Spectra (XPS), and Scanning Electron Microscopy-Energy Dispersive X-ray Spectra (SEM-EDX) analysis. X-ray photon spectra results confirmed the formation of the composites. Composites of MWCNT were used in dye-sensitized solar cells (DSSCs) as counter electrodes and exhibited short-circuit photocurrent densities of 11.19, 10.70 and 8.54 mA/cm² for PANI/MWCNT, PTh/MWCNT and PEDOT/CNT, respectively.     

Electrochemical fabrication of polythiophene film coated metallic nanowire arrays

Metallic gold (Au) and silver (Ag) nanowire arrays coated with polythiophene (PTh) films were fabricated by successive electrochemical depositions of PTh and metal into the pores of a microporous alumina membrane. The diameter of the composite nanowires was 200 nm and that of the metallic nanowires was about 100 nm. They are adhered to a thin gold film and aligned in a high density of ca. 10¹⁰ wires/cm². The morphology of the composite nanowires has been characterized by an optical microscope, Raman spectroscopy, scanning and transmission electron microscopies. Their electrochemical property has also been investigated.     

Ethylene glycol oxidation on Pt and Pt-Ru nanoparticle decorated polythiophene/multiwalled carbon nanotube composites for fuel cell applications

A novel supporting material containing polythiophene (PTh) and multiwalled carbon nanotubes (MWCNTs) (PTh-CNTs) is prepared by in?situ polymerization of thiophene on carbon nanotubes using FeCl(3) as oxidizing agent under sonication. The prepared polythiophene/CNT composites are further decorated with Pt and Pt-Ru nanoparticles by chemical reduction of the corresponding metal salts using HCHO as reducing agent at pH = 11 (Pt/PTh-CNT and Pt-Ru/PTh-CNT). The fabricated composite films decorated with nanoparticles were investigated towards the electrochemical oxidation of ethylene glycol (EG). The presence of carbon nanotubes in conjugation with a conducting polymer produces a good catalytic effect, which might be due to the higher electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces, which allows higher dispersion of Pt and Pt-Ru nanoparticles. Such nanoparticle modified PTh-CNT electrodes exhibit better catalytic behavior towards ethylene glycol oxidation. Results show that Pt/PTh-CNT and Pt-Ru/PTh-CNT modified electrodes show enhanced electrocatalytic activity and stability towards the electro-oxidation of ethylene glycol than the Pt/PTh electrodes, which shows that the composite film is more promising for applications in fuel cells.     

Synthesis and characterization of polythiophene-modified TiO<Subscript>2</Subscript> nanotube arrays

The highly ordered and uniform TiO₂ nanotube arrays were fabricated by anodic oxidation method and PTh(polythiophene)/TiO₂ nanotube arrays electrode were obtained by electrochemical polymerization. X-ray powder diffraction (XRD) analysis confirmed the formation of TiO₂ phase. The morphologies and optical characteristics of the TiO₂ nanotube arrays were studied by scanning electron microscope (SEM), UV-Vis absorption spectra and Raman spectra. The results demonstrate that the PTh/TiO₂ electrode could enlarge the visible light absorption region and increase the photocurrent in visible region. The modified TiO₂ electrode with light-to-electric energy conversion efficiency of 1·46%, the short-circuit current density of 4·52 mAcm^− 2, open-circuit voltage of 0·74 V and fill factor of 0·44, were obtained.     

聚噻吩及其衍生物热电材料研究进展

近来,聚合物热电材料因其成本低、资源丰富、热导率低等优势被认为是最有前途的热电材料之一。聚噻吩及其衍生物是研究较为广泛的一类聚合物热电材料。综述了近年来聚噻吩、聚噻吩衍生物以及聚噻吩基/无机复合热电材料在热电领域的研究进展。已有研究表明,聚噻吩及其衍生物热电材料具有高的Seebeck系数,其See-beck系数与电导率通常是此消彼长的关系。通过制备低维材料,与高电导率的无机纳米材料复合以及适度掺杂等方法可有效提高聚噻吩及其衍生物的热电性能。