聚(3,4-乙撑二氧噻吩)导电织物的制备、结构及其电致变色性能

本文采用原位聚合法, 以耐酸性好的涤纶为基底, 制得了聚(3,4-乙撑二氧噻吩)/涤纶复合导电织物[Poly(3,4-ethylenedioxythiophene)/conducting terylene textile, PEDOT/CTT], 分析了该导电织物的形貌、导电性能及结构, 并对其电致变色性能进行了初步测试. 实验结果表明, 所得到的PEDOT/CTT具有良好的导电性和一定的电致变色性能, 有望在全固态电致变色织物的制备中获得应用.     

二甲基亚砜改性聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸薄膜的研究及应用进展

二甲基亚砜(DMSO)被称为“万能溶剂”,除了在化学、医学、化妆品等领域的常规应用,在有机电子领域也有展现出特色应用。 聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)是一类卓越的水分散性导电聚合物材料,具有优异的可加工性、混合性、生物兼容性、成膜性以及可商业规模生产等优势,被广泛应用于抗静电涂层、透明电极、有机太阳能电池、超级电容、生物传感等新材料和绿色能源领域。 DMSO对调控PEDOT:PSS薄膜的形貌、导电、热电、功函,界面接触、力学、自修复等性能具有重要作用。 基于我们团队及国内外学者在本领域的研究成果,本文系统综述了DMSO对PEDOT及其衍生物:PSS(PEDOTs:PSS)作用的效果及其机制,探讨了应用中面临的问题与挑战。     

基于聚3,4-乙撑二氧噻吩和1-芘丁酸构建的新型铁卟啉仿生传感器及其对邻苯二酚的催化研究

利用π-π共轭效应,将1-芘丁酸(PBA)与导电高聚物聚3,4-乙撑二氧噻吩(PEDOT)相连,并通过Zr4+与羧基形成的配位键将羟基铁卟啉(Hematin)与PBA相连接,将Hematin固定于电极上,构建出一种制备过程简单的新型传感器(GCE/PEDOT/PBA/Hematin)。为了检验这种仿生传感器的稳定性和灵敏度,通过循环伏安法(CV)、交流阻抗法(EIS)和时间电流曲线法(i-t)等各种技术,将其应用于电化学检测中。CV扫描证实在充分除氧的PBS缓冲液中,GCE/PEDOT/PBA/Hematin出现一对准可逆的氧化还原峰,其电子转移速率常数约为4.8 s!1,说明聚合于电极上的PEDOT膜增加了Hematin的电子转移速率。另外,通过i-t曲线检测邻苯二酚,在邻苯二酚浓度5×10!7~2×10!4mol/L范围内,其与催化电流强度呈线性相关,i=0.018C+0.006(R=0.9998),检测灵敏度为0.258μA(μmol·cm2),检出限为0.33 nmol/L(S/N=3),证明此仿生传感器稳定,简单且灵敏度高。     

聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸盐热电性能的 提升策略研究进展

近十年,有机聚合物及其复合热电材料与柔性器件取得了显著进展,在废热回收利用、可穿戴电子学、软体机器人和物联网等领域有广泛的应用.其中,聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)是迄今研究最多也是性能最高的聚合物体系.本文对近年来有关PEDOT:PSS热电性能有效提升主要策略的文献报道进行了总结.首先,从PEDOT:PSS的二次掺杂/去掺杂、酸或碱处理和离子液体处理方面等,重点论述了掺杂/去掺杂策略的研究进展;然后,分别从改善聚集态结构、构筑PEDOT微纳米结构和与碳纳米材料复合等3个方面,重点介绍了采用此3种策略提升PEDOT:PSS热电性能的研究进展;最后,对该领域进行总结,提出了开展进一步研究的建议,并对其未来发展前景进行展望.     

纳米纤维素/聚3,4-乙撑二氧噻吩复合薄膜的制备及电致变色性能

以棉浆粕为原料,采用硫酸溶胀结合超声波处理的方法制备了纳米纤维素(NC).在纳米纤维素的水分散液中加入3,4-乙撑二氧噻吩单体,以过硫酸铵为氧化剂,采用原位化学氧化法制得了纳米纤维素/聚3,4-乙撑二氧噻吩(NC/PEDOT)纳米复合物.对NC和NC/PEDOT复合物进行扫描电镜、透射电镜和红外光谱分析.将纳米复合物的水分散液滴涂在氧化铟锡(ITO)玻璃表面形成复合薄膜,考察不同纳米纤维素含量对NC/PEDOT复合薄膜电致变色性能的影响.结果表明,NC呈棒状,平均直径为20 nm,长度为100~300nm;NC/PEDOT复合物中PEDOT均匀包覆在NC表面形成核壳结构,平均直径为30 nm;复合薄膜中当NC含量为60%时,其电致变色性能最好,具有最高的对比度(24.4%),最短的响应时间(1 s),最高的着色效率(51.8 cm~2/C).     

含3,4-乙撑二氧取代基的聚三噻吩衍生物的合成与表征

通过Stille反应合成了3,′4′-乙撑二-氧2,2′∶5,′2″-三噻吩,并以其作为单体,在0~5℃下,以FeCl3为氧化剂,在氯仿溶液中合成了3种聚(3,′4′-乙撑二氧-2,2′∶5,′2″-三噻吩)。并采用紫外-可见光谱(UV-Vis)、傅里叶红外光谱(FT-IR)、凝胶色谱(GPC)、循环伏安(CV)、透射电镜(TEM)和热重分析(TGA)对聚合物进行了表征。同时讨论了乙撑二氧取代基和FeCl3用量对聚合物性质的影响。结果表明:聚合物的紫外最大吸收为466~474 nm,数均分子量为3.4×103~3.6×103,能隙大约为2.05 eV,热分解温度为110℃。     

基于聚(3,4-乙烯二氧噻吩)/天青Ⅰ复合物薄膜和纳米金修饰的电流型甲胎蛋白免疫传感器的研究

研制了一种基于聚(3,4-乙烯二氧噻吩)(PEDOT)与天青Ⅰ(AzureⅠ)为基体的电化学免疫传感器,可灵敏检测甲胎蛋白(AFP)。在铂盘电极表面,电化学聚合PEDOT为基体,利用静电组装技术固定AzureⅠ和纳米金颗粒(nanoAus),将甲胎蛋白抗体(anti-AFP)组装到nanoAus的表面。采用辣根过氧化物酶(HRP)封闭非特异性吸附位点,制得电流型AFP免疫传感器。采用循环伏安、扫描电镜技术研究组装过程及电极性质,探讨了影响免疫传感器性能的因素。在优化实验条件下,电极响应与AFP的浓度在0.01~120μg/L的范围内呈线性关系,检出限为0.003μg/L。取临床血清样品用本方法检测AFP含量,得到的结果与临床常用的ELISA法得到的结果无显著性差异。     

银纳米颗粒/聚(乙撑二氧噻吩)修饰的硅纳米线阵列的合成及可见光催化性能研究

硅纳米线阵列由于其较强的光吸收能力及硅材料的丰富储量,被认为是最具大规模应用潜力的可见光光催化剂.针对硅材料在水相环境中不稳定这一瓶颈问题,本文提出了对硅纳米线阵列"先稳定、再活化"的修饰策略.通过在硅纳米线表面修饰聚(乙撑二氧噻吩)使其稳定,之后再修饰银纳米颗粒以提高光催化效率,得到了高效、稳定的可见光光催化剂.并通过研究聚(乙撑二氧噻吩)的厚度及银纳米颗粒的担载量对光催化剂性能的影响,得到了最佳的修饰条件.     

原位聚合聚(3,4-乙烯二氧噻吩):π共轭聚电解质应用于聚合物太阳能电池空穴传输层

以带磺酸基团的π共轭聚电解质为模板,采用化学氧化还原方法制备了在水相中稳定分散的聚(3,4-乙烯二氧噻吩)(PEDOT)与聚电解质的复合物,并用作聚合物太阳能电池的空穴传输层.通过傅里叶变换红外光谱(FTIR)、紫外可见光谱(UV-Vis)、紫外光电子能谱(UPS)、原子力显微镜(AFM)、透射电子显微镜(TEM)和接触角等对聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸(PEDOT:PSS)和复合物薄膜的形貌和光电性能进行测试与表征.结果表明,相比于PEDOT:PSS,PEDOT:聚电解质复合物作为空穴传输层,具有合适的能级结构、高达95%的透光率(30 nm)、更疏水的表面形貌以及更高的空穴迁移率,有利于与活性层形成欧姆接触并提高空穴的注入和收集效率,进而提高器件的光伏性能.     

聚-3,4-乙烯二氧噻吩导电聚合物纳米粒子的制备及性能

采用反向胶束合成法, 以二乙基磺基琥珀酸钠(AOT)形成的反胶束为模板制备了导电聚合物聚-3,4-乙烯二氧噻吩(PEDOT)纳米粒子. 用紫外-可见-近红外光谱、红外光谱、X射线光电子能谱、扫描电子显微镜及透射电镜等手段对PEDOT粒子进行了表征. 研究了纳米粒子的导电性能并采用石英微天平(QCM)对纳米粒子的气敏特性进行了分析, 对相应导电机理及气体敏感机理进行了讨论.     

Determination of Uric Acid in the Presence of Ascorbic Acid Using Poly(3,4‐ethylenedioxythiophene)‐Modified Electrodes

A poly(3,4‐ethylenedioxythiophene) (PEDOT) modified glassy carbon electrode (GCE) was used to determine uric acid in the presence of ascorbic acid at physiological pH facilitating a peak potential separation of ascorbic acid and uric acid oxidation (ca. 365 mV), which is the largest value reported so far in the literature. Also, an analytical protocol involving differential pulse voltammetry has been developed using a microchip electrode for the determination of uric acid in the concentration range of 1 to 20 μM in presence of excess of ascorbic acid.     

SYNTHESIS OF SOLUBLE POLY（3,4-DIHYDROXY-o-TOLYLENE）： REDOX POLYMER

Conventional chloromethylation, paraformaldehyde/hydrogen chloride in acetic acid medium, was applied to 1,2- dimethoxybenzene. Chloroform-soluble poly（3,4-dimethoxy-o-tolylene） was obtained with an intrinsic viscosity of 0.034 dL g^-1. The polymer was evaluated as a condensation redox polymer precursor formed by a Friedel-Crafts reaction. Cleavage of the methoxy groups present in this polymer resulted in poly（3,4-dihydroxy-o-tolylene） which manifested a great air-oxidation resistance. The redox property of the latter polymer was found to be 1017 mV by potentiometric titration with 0.05 N ceric ammonium nitrate at 25℃. This midpotential was compared to that of catechol, a monomeric analogue, under the same titration conditions.     

Properties of nanometric and submicrometric multilayered films of poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole)

Multilayered films formed by 3, 5 and 7 alternated layers of poly(3,4-ethylenedioxythiophene) and poly(N-methylpyrrole) have been prepared by chronoamperometry under a constant potential of 1.4 V using a layer-by-layer electrodeposition technique. In order to examine influence of the interface:bulk dimensional ratio, the thickness of the yielded films was reduced from the submicrometric to the nanometric scale by decreasing the polymerization time of each layer from 100 s to 10 s. The electroactivity, electrochemical characteristics and morphologies of the resulting multilayered films have been compared with those obtained for both single-component poly(3,4-ethylenedioxythiophene) films prepared using identical experimental conditions and previously reported multilayered films with thickness within the micrometric scale [Estrany F, Aradilla D, Oliver R, Alemán C. Eur Polym J 2007;43:1876].     

Micro-patterning of vapor-phase polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) using ink-jet printing/soft lithography

Highly conductive and transparent poly(3,4-ethylenedioxythiophene) (PEDOT) thin films can be prepared effectively via vapor-phase polymerization (VPP) with the addition of imidazole (Im) based derivatives. The addition of Im that has one and/or two alkyl substituents significantly improved the electrical conductivity of PEDOT thin films. In an effort to develop a facile PEDOT micro-patterning method, we investigated ink-jet printing and soft lithography. The procedure of oxidant patterning with a weak base followed by VPP of a 3,4-ethylenedioxythiophene (EDOT) monomer provides an effective and simple method for micro-patterning of an intrinsic conductive polymer (ICP).     

A Novel Superabsorbent Composite Based on Poly(Aspartic Acid) and Organo-Kaolin

A novel superabsorbent composite of poly(aspartic acid)(PAsp)/organo-kaolin was prepared by the nonaqueous inverse-phase suspension method and characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The equilibrium swelling ratio of the composite could be effectively improved by the introduction of organo-kaolin and when the organo-kaolin content is 3?wt% the maxima were achieved, 753 for distilled water and 125 for 0.9?wt% NaCl aq. solution. Salt resistance, pH sensibility and temperature response were also studied considering the practical application of the PAsp/organo-kaolin superabsorbent composite.     

Conducting poly(3,4-ethylenedioxythiophene)-montmorillonite exfoliated nanocomposites

Exfoliated nanocomposites formed by poly(3,4-ethylenedioxythiophene) and different concentrations of non-modified montmorillonite (bentonite), which range from 1% to 10% w/w, have been prepared by anodic electropolymerization in aqueous solution. Analyses of the electrochemical and electrical properties reveal that the electroactivity of the nanocomposites is higher than that of the individual homopolymer, while the electrical conductivity of the two systems is practically identical. On the other hand, the exfoliated distribution of the clay in the polymeric matrix and the morphology of the prepared materials have been characterized using transmission electron microscopy, X-ray diffraction and atomic force microscopy. The overall of the results represents a significant improvement with respect to other nanocomposites constituted by conducting polymers and clays, including those involving poly(3,4-ethylenedioxythiophene), and evidences the reliability of the preparation procedure employed in this work.     

聚乙烯醇/聚吡咯复合导电水凝胶应变传感器的制备及性能

以聚乙烯醇(PVA)为原料, 植酸(PA)和氨基-聚倍半硅氧烷(NH₂-POSS, NP)为交联剂, 通过冻融循环法制得PVA/PA/NP复合水凝胶, 再以其为模板, 通过吡咯的原位聚合制得PVA/PA/NP-PPy复合导电水凝胶, 克服了聚吡咯材料易脆、 疏水的特性, 进一步改善了水凝胶的导电性和灵敏性. 循环拉伸实验结果表明该水凝胶具有良好的自回复能力, 电导率高达7.53 S/m, 从I-V曲线可知其作为柔性可穿戴应变传感器的最高检测电流可达 9.029 mA, 灵敏度因子可达6.796, I-T曲线表明该传感器可以准确地通过电流信号变化来监测人体的各种微小运动.     

Investigation of the doping efficiency of poly(styrene sulfonic acid) in poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) dispersions by capillary electrophoresis

CE can efficiently separate poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) complexes and free PSS in dispersions and can be used to estimate the degree of PSS doping. We investigated the doping efficiency of PSS on PEDOT in dispersions using CE and its effect on the conductivity of the resulting PEDOT/PSS films. Results of this study indicate that dispersions containing 1:2.5–3 EDOT:PSS feed ratio (by weight) exhibiting 72–73% PSS doping generate highly processable and highly conductive films. Conductivity can be optimized by limiting the time of reaction to 12 h. At this point of the reaction, the PEDOT/PSS segments, appearing as broad band in the electropherogram, could still exist in an extended coil conformation favoring charge transport resulting in high conductivity. Above a threshold PEDOT length formed at reaction times longer than 12 h, the PEDOT/PSS complex, appearing as spikes in the electropherogram, most likely have undergone a conformational change to coiled core‐shell structure restricting charge transport resulting in low conductivity. The optimal conductivity (5.2 S/cm) of films from dispersions synthesized for 12 h is significantly higher than those from its commercial equivalent Clevios P and other reported values obtained under similar conditions without the addition of codopants.