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.     

石墨烯/聚3，4-乙烯二氧噻吩复合物的电化学制备及其在超级电容器中的应用

首次提出了一种在离子液体中在石墨烯表面用恒电流法聚合3,4-乙烯二氧噻吩(EDOT)单体制备石墨烯/聚3,4-乙烯二氧噻吩(石墨烯/PEDOT)复合物的方法。用原子力显微镜、扫描电镜等技术表征证明石墨烯/PEDOT复合物是由PEDOT纳米谷粒状颗粒分散在石墨烯片表面而组成的。将该复合物用作超级电容器电极材料时,在1.0 A.g-1的充放电比电流下得到的比电容值为181 F.g-1。同时,该材料还显现出较好的充放电可逆性和稳定性。     

基于石墨烯/金纳米复合材料的无酶葡萄糖传感器

以抗坏血酸(AA)为还原剂,通过一步还原法将氧化石墨烯和氯金酸同时还原,合成石墨烯/金纳米复合材料,并直接滴涂于玻碳电极表面,构建基于石墨烯/金纳米复合材料的无酶葡萄糖传感器。采用循环伏安法和线性扫描伏安法对传感器的性质进行了研究。结果表明,该传感器能催化葡萄糖的氧化,且其氧化峰电流随葡萄糖浓度的增大而增大。测定葡萄糖的线性范围为0.01~2.5mmol/L(R=0.9964),检出限(S/N=3)为3μmol/L。对同一浓度的葡萄糖溶液平行测定8次,其电流强度的相对标准偏差(RSD)为2.6%。该传感器制作简单、稳定性好,将其用于葡萄糖注射液的检测,方法灵敏,其加标回收率为92.9%。     

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。     

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.     

石墨烯/纳米金复合材料的无酶葡萄糖生物传感器制备

以抗坏血酸(AA)为还原剂,通过同步还原法制得石墨烯/纳米金复合材料.采用电化学方法,构建了一种基于石墨烯/纳米金复合材料修饰电极的无酶葡萄糖生物传感器.实验中,通过伏安法考察了不同修饰电极在葡萄糖溶液中的电化学行为.同时,探讨了溶液中OH-离子强度、溶解氧、扫描初始电位及石墨烯与纳米金的比例对传感器响应特性的影响.在...     

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.     

反向胶束法制备聚3,4-乙烯二氧噻吩纳米粒子的光电性能和热稳定性

采用聚合和掺杂同时进行的反向胶束体系制备了粒径分散较小的聚3,4-乙烯二氧噻吩(PEDOT)纳米粒子, 利用紫外-可见光光谱(UV-Vis)、X射线衍射(XRD)和扫描电子显微镜(SEM)等分析方法对纳米粒子进行了表征. 实验结果发现, 氧化剂用量、超声处理、聚合温度及掺杂程度对PEDOT纳米粒子的形貌、电性能及热稳定性有不同程度的影响. 根据实验结果对反向胶束法制备PEDOT纳米粒子过程进行优化发现, 在PEDOT纳米粒子聚合过程中, 甲基苯磺酸有效掺杂浓度约为0.17 mol/L时, PEDOT链的取向最规则, 在6.7°, 12.7°, 25°出现衍射峰, 掺杂剂的有效掺杂使得纳米粒子中分子链的取向不同, 并可以获得较高的电导率(>100 S/cm)的PEDOT纳米粒子, 当粒子的尺寸小于20 nm后电导率降低; 热失重法(TG)分析结果表明, PEDOT纳米粒子的热稳定性比普通块材好, 掺杂剂浓度对纳米粒子的热稳定性有一定影响.     

聚(3,4-乙烯二氧噻吩)∶聚苯乙烯磺酸/无机纳米复合材料的制备及应用

聚(3,4-乙烯二氧噻吩)∶聚(苯乙烯磺酸)(PEDOT∶PSS)是一种水溶性导电高分子体系,具有易加工、高透光率及柔韧性等优点,但其应用范围仅限于作为电子器件的柔性电极材料。为了进一步扩大PEDOT∶PSS的应用范围,将无机纳米材料引入该体系实现材料的多功能化是较为有效的方法。本文首先介绍了PEDOT∶PSS/无机纳米复合材料最常用的四种制备方法,即原位法、共混法、自组装法、插层复合法,分别介绍了每种制备方法的原理和特点,并阐述了研究人员对复合材料的结构设计思路及引入的无机相对材料性能的影响。随后,综述了PEDOT∶PSS/无机纳米复合材料在传感器、太阳能电池、超级电容器、热电发电机等领域中应用的最新进展。最后指出了目前在PEDOT∶PSS/无机纳米复合材料的研究中面临的挑战,并对该材料的研究方向和发展趋势进行了展望。     

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.     

聚乙撑二氧噻吩/二氧化锰纳米复合物的界面聚合制备及其电化学性能

采用界面聚合法制备聚3,4-乙撑二氧噻吩/二氧化锰(PEDOT/MnO2)纳米复合物. 通过红外(IR)光谱、X射线衍射(XRD)、BET比表面积、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对样品进行表征. 结果表明, 产物是具有丰富的多孔孔道结构的无定型纳米材料, 孔径主要分布在5-25 nm范围内, 比表面积可达98 m2·g-1. 同时用循环伏安(CV)、恒流充放电和交流阻抗(EIS)等电化学测试表明, 在0.5 mol·L-1 Na2SO4溶液中, -0.2 - 0.8 V(vs SCE)的电化学窗口下, PEDOT/MnO2纳米复合物显示出良好的电化学性能, 当电流密度为0.5 A·g-1时, 所制备的PEDOT/MnO2单电极比容量达196.3 F·g-1, 500次循环后样品放电比容量保持90%左右.     

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).     

基于聚对苯二甲酸乙二醇酯薄膜的石墨烯/金纳米粒子/葡萄糖氧化酶柔性电极的制备及检测葡萄糖

采用化学气相沉积法生长多晶石墨烯(Graphene, G),转移至聚对苯二甲酸乙二醇酯(PET)薄膜表面,通过控制金溶胶蒸发速率,在多晶石墨烯表面组装均匀分布的亚单层金纳米粒子(AuNPs);然后修饰巯基乙酸,通过共价交联反应将葡萄糖氧化酶固定于AuNPs表面,构建基于PET膜的石墨烯/金纳米粒子/葡萄糖氧化酶(G/AuNPs/GOD)柔性电极.此电极在工作电位0.6 V(vs.SCE电极)、pH 7.0磷酸盐缓冲溶液、室温25℃条件下,差分脉冲伏安法响应电流与被测葡萄糖浓度在0.05~10.55 mmol/L范围内呈线性关系,线性方程为I(108A)=0.2629 C(mmol/L)+1.4149,线性相关系数 r=0.9955,检出限1 μmol/L (3σ). G/AuNPs/GOD柔性电极的制备可为特定环境和可穿戴设备的葡萄糖检测提供了新的途径和方法,拓展了葡萄糖检测的应用范围.     

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。     

水下超疏油聚(3,4-乙烯基二氧)噻吩薄膜的制备简

以离子液体溴化(1-己基-3-甲基咪唑盐)作为电解质和掺杂剂采用电化学一步法制备了微纳米复合结构的聚(3,4-乙烯基二氧噻吩)薄膜,薄膜由槽内排布着纳米珠链的棒状结构组成. 研究表明,通过控制电流密度的大小,可以调节棒状结构和珠状结构的平均直径. 离子液体中的咪唑阳离子和对阴离子均掺杂到聚合物中,该薄膜具有可逆的电化学活性及水下超疏油特性.     

A Review of Glucose Biosensors Based on Graphene/Metal Oxide Nanomaterials

In recent years, considerable attention has been paid to developing economical yet rapid glucose sensors using graphene and its composites. Recently, the excellent properties of graphene and metal oxide nanoparticles have been combined to provide a new approach for highly sensitive glucose sensors. This review focuses on the development of graphene functionalized with different nanostructured metal oxides (such as copper oxide, zinc oxide, nickel oxide, titanium dioxide, iron oxide, cobalt oxide, and manganese dioxide) for use as glucose biosensors. Additionally, a brief introduction of the electrochemical principles of glucose biosensors (including amperometric, potentiometric, and conductometric) is presented. Finally, the current status and future prospects are outlined for graphene/metal oxide nanomaterials in glucose sensing.     

Electrochemical recognition and trace-level detection of bactericide carbendazim using carboxylic group functionalized poly(3,4-ethylenedioxythiophene) mimic electrode

The electrochemical recognition and trace-level detection of bactericide carbendazim (MBC) in paddy water and commercial juice were realized using carboxylic group functionalized poly(3,4-ethylenedioxythiophene) (PC4-EDOT-COOH) film electrode. PC4-EDOT-COOH film was prepared by one step, low-cost, and green electrosynthesis in aqueous microemulsion system and characterized by FT-IR, cyclic voltammetry, UV–vis and SEM. In comparison with poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(hydroxymethylated-3,4-ethylenedioxylthiophene) (PEDTM), PC4-EDOT-COOH exhibited the best electrochemical recognition towards MBC and the recognition mechanism was proved by quantitative calculation. Sensing parameters such as pH values, accumulation potential, accumulation time, supporting electrolyte, and scan rate on the current response of MBC were discussed. In addition, the sensor can be applied to quantification of MBC in the concentration range of 0.012–0.35 μM with a low detection limit of 3.5 nM (S/N = 3). Moreover, PC4-EDOT-COOH film electrode showed good stability, high selectivity, and satisfactory anti-interference ability. Satisfactory results indicated that PC4-EDOT-COOH film is a promising sensing platform for the trace-level analysis of bactericide residue carbendazim in agricultural crops and environment.     

Cellular adhesion and proliferation on poly(3,4-ethylenedioxythiophene): Benefits in the electroactivity of the conducting polymer

Cell adhesion and proliferation in poly(3,4-ethylenedioxythiophene), an electroactive polythiophene derivative generated by anodic polymerization, has been investigated. Results show that epithelial cells Hep-2 present significant activity on the surface of poly(3,4-ethylenedioxythiophene) electrodeposited on stainless steel electrodes, no sign of cytotoxicity being detected for this conducting polymer. Indeed, seeded and cultured cells bound better to poly(3,4-ethylenedioxythiophene) than to uncoated stainless steel, the latter substrate being used as a control. Furthermore, the electrochemical characteristics of poly(3,4-ethylenedioxythiophene) covered with cells was determined in different biological media using cyclic voltammetry experiments. Results reveal a significant increase in the electroactivity of this material when it is covered with a cellular monolayer. The overall of the results evidences not only the biocompatibility of poly(3,4-ethylenedioxythiophene) with Hep-2 cells but also their electrocompatibility.     

Electrochemical Determination of Dopamine Using a Poly(3,4-Ethylenedioxythiophene)-Reduced Graphene Oxide-Modified Glassy Carbon Electrode

Poly(3,4-ethylenedioxythiophene) was deposited on a reduced graphene oxide-decorated glassy carbon electrode through an electrochemical polymerization. The resulting glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode was applied as an electrochemical biosensor for the determination of dopamine in the presence of ascorbic acid and uric acid. The material deposited on glassy carbon electrode was investigated in terms of morphology and structural analysis. The comparison of electrochemical behavior of the glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode with the glassy carbon electrode-graphene oxide, glassy carbon electrode-reduced graphene oxide, and glassy carbon electrode-poly(3,4-ethylenedioxythiophene) electrodes exhibited high electrocatalytic activity for dopamine detection. Electrochemical kinetic parameters of glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene), including the charge transfer coefficient α (0.49) and electron transfer rate constant k_s (1.04), were determined and discussed. The glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode was studied for the determination of dopamine by differential pulse voltammetry and exhibited a linear range from 19.6 to 122.8?µM with a sensitivity of 3.27?µA?µM^?1?cm^?2 and a detection limit of 1.92?µM. The developed biosensor exhibited good selectivity toward dopamine with high reproducibility and stability.