聚乙撑二氧噻吩的导电性及现场ESR响应的研究

聚乙撑二氧噻吩(PEDOT)因为具有很高的稳定性和导电性，近年来受到了广泛 的注意并开始在许多方面得到实际应用．电化学聚合方法具有操作简便、易于控制 等优点．本文采用恒电位电化学聚合方法，在水溶液中Pt电极上制备了聚乙撑二氧 噻吩．研究了单体浓度、支持电解质种类、聚合电位等因素对聚合得到的PEDOT膜 导电性的影响．首次运用电化学现场ESR技术研究了水溶液中PEDOT膜的ESR响应， 结合电化学现场的膜电阻测量研究了PEDOT膜的导电性随所加电位的变化规律．结 果表明，PEDOT膜随不同电位的导电性的变化规律符合极化子—双极化子理论．     

聚乙撑二氧噻吩修饰电极的电化学行为及对抗坏血酸的电催化作用

研究了聚乙撑二氧噻吩修饰电极在水溶液中的电化学行为及对抗坏血酸的电催化作用,实验表明抗坏血酸在聚乙撑二氧噻吩修饰电极上的氧化峰电位为+0.23V,较其在铂电极上的氧化峰电位负移220mV.在1.0×10^-1～1.0×10^-1mol/L浓度范围内,峰电流和抗坏血酸的浓度有线性关系,可用于水果等样品中抗坏血酸的测定。     

磁性离子液体中聚乙撑二氧噻吩/多壁碳纳米管纳米复合材料的球磨法制备及表征

以磁性离子液体1-丁基-3-甲基咪唑四氯化铁盐([bmim]FeCl₄)为介质, 将多壁碳纳米管(MWCNTs)机械球磨分散在其中形成[bmim]FeCl₄/MWCNTs凝胶后, 加入乙撑二氧噻吩(EDOT)单体, 利用阴离子 的氧化性进行原位聚合, 球磨法制备了均匀包覆不同含量MWCNTs的聚乙撑二氧噻吩/多壁碳纳米管(PEDOT/MWCNTs)纳米复合材料. 并以傅里叶红外光谱(FT-IR)、扫描电镜(SEM)和透射电镜(TEM)对PEDOT/MWCNTs的结构与形貌进行了表征|在0.5 mol/L硫酸溶液中, 用循环伏安测试(CV)研究了PEDOT/MWCNTs的电化学行为|采用四探针仪测定了PEDOT/MWCNTs的电导率|热重分析(TGA)研究了PEDOT/MWCNTs的热稳定性. 结果表明, PEDOT 纳米颗粒均匀包覆于MWCNTs表面, 形成了核壳结构|PEDOT与MWCNTs之间的共轭作用随着MWCNTs含量的增加而增强. MWCNTs的质量分数为30%的PEDOT/MWCNTs的电导率出现峰值, 达到7.46 S/cm, 且电化学活性最好. MWCNTs的质量分数为10%时, PEDOT/MWCNTs的热稳定性相对于PEDOT显著提高.     

聚乙撑二氧噻吩阳极降解的研究

研究了聚乙撑二氧噻吩(PEDOT)膜在水溶液中的阳极降解过程. 研究发现PEDOT的阳极过程可以分为p掺杂区[电位范围－0.3～0.5 V (相对于饱和甘汞电极; vs. SCE)]、过渡区[电位范围0.6～1 V (vs. SCE)]、过氧化区[电位范围1.2～1.6 V (vs. SCE)]三个电位区域. 用电化学阻抗谱法、循环伏安法、红外光谱技术、膜电阻测量以及电子自旋共振技术分别研究了PEDOT膜在这三个电位区域的行为. 结果表明: PEDOT膜在这三个电位区域的性质有明显不同. 在p掺杂区PEDOT膜的官能团、共轭结构、导电性均保持, 即在这个电位区发生可逆的掺杂/脱掺杂反应, 膜几乎不降解. 在过渡区和过氧化区, PEDOT膜均发生了降解. 与传统的导电聚合物在高电位的阳极降解的过氧化过程不同, 我们认为膜在较高电位(过渡区)发生一个驰豫过程, 该过程使得膜的官能团改变, 但是膜的共轭结构和导电性均保持; 而在更高的电位区(过氧化区)膜的降解和一般意义的过氧化降解相同, 此时膜的官能团、共轭结构、导电性均发生不可逆的破坏.     

Fe(ClO_4)_3氧化合成聚乙撑二氧-三噻吩

分别以Fe(Cl O4)3、FeCl3、Fe2(SO4)3作为氧化剂,对3′,4′-乙撑二氧-2,2′∶5′,2″-三噻吩(TET)进行了化学氧化聚合,并研究了聚合条件对聚合物结构和电化学性能的影响。利用红外光谱、紫外光谱、X射线衍射对聚合物进行了表征,采用循环伏安、恒电流充放电等电化学方法研究了聚合物的电化学性能。结果表明:当TET与Fe(Cl O4)3的摩尔比为1∶4,反应温度为18℃,反应时间为12 h时,聚3′,4′-乙撑二氧-2,2′∶5′,2″-三噻吩(PTET)具有更好的共轭结构和电化学性能,导电率可达1.47 S/m,比电容可达133 F/g。     

固相法制备D-A-D型共轭聚合物/MnO2复合物及光催化性能研究

分别采用固相法即固相化学法和固相物理共混法制备了给体-受体-给体(D-A-D)型共轭聚合物聚(2,5-二(2-(3,4-乙撑二氧噻吩))基哒嗪)与纳米MnO2的复合物(3,4-乙撑二氧噻吩环作为给体单元;哒嗪环作为受体单元),采用FT-IR、UV-vis、XRD、SEM等手段对复合物的结构和形貌进行了表征,并研究了该类...     

3-甲基噻吩和3-氯噻吩的电化学共聚

3-甲基噻吩和3-氯噻吩首次三氟化硼乙醚溶液中实现了电化学共聚。共聚物的分子结构通过电化学分析、红外和拉曼光谱得到了证实。实验结果表明：单体投料比对共聚物的结构和电化学性质有很大的影响;共聚物比3-甲基噻吩和3-氯噻吩的均聚物具有更大的充放电电容和更可逆的氧化还原性质。     

暗场显微镜下原位监测GNR/PEDOT在ITO界面上组装成膜过程

研究采用电化学聚合法,在中性水溶液中以3,4-乙烯二氧噻吩(EDOT)为反应液,在金纳米棒(GNR)修饰的ITO上聚合成PEDOT导电薄膜,并对该体系的稳定性进行了研究。利用暗场光学显微镜原位实时观察了聚合过程中纳米粒子掺杂的导电聚合物的微结构形貌不断进化,同时原位研究了该体系的光电性质。随着反应时间的增加,掺杂了纳米粒子的PEDOT薄膜的微结构形貌不断进化,从分散的颗粒状态向连续的树枝状态转变,最后成有些微高低起伏的薄膜状。     

水溶液中聚噻吩的电化学变色效应

水溶液中聚噻吩电化学变色是其氧化还原反应的颜色效应, 电化学反射光谱可现场研究电化学变色特性。聚噻吩电化学变色的转换时间为10—20 ms, 寿命达10~4次数量级, 保留时间有数分钟。因此, 聚噻吩在水溶液中也可制成较理想的电化学变色显示器。     

掺杂PEDOT：PSS空穴传输层在钙钛矿太阳能电池中的应用

钙钛矿太阳能电池(PSCs)因易于制备、生产成本低和能量转换效率高而受到广泛关注。聚乙撑二氧噻吩-聚(苯乙烯磺酸盐)(PEDOT∶PSS)由于具有易低温加工、透光度高和适宜空穴迁移率等特点而成为PSCs中空穴传输层的研究热点。本文简述了倒置PSCs的结构及工作原理,重点介绍了掺杂PEDOT∶PSS空穴传输层在PSCs领域的研究现状。分别从有机化合物掺杂剂、无机化合物掺杂剂和表面活性剂掺杂剂三个类别概述了掺杂PEDOT∶PSS空穴传输层对PSCs性能的影响。最后,对该领域存在的问题提出潜在措施以改善PEDOT∶PSS掺杂层在PSCs中的应用。     

Study on polymerization and structure of polydiphenylamine

The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent uniform polymer film which exhibits mutiple colour variation(yellow-green-blue) in a wide range of potential scan. The polymerization mechanism and the structure of the polymer were studied by cyclic voltammetry, FT-IR and in situ ESR. The results indicate that the electrochemical polymerization of diphenylamine belongs to a cationic radical polymerization process. During electrolysis, only oligomers were initialy produced, then polymer film was formed on the electrode surface. The electropolymerization performs via the 4,4' C-C phenyl-phenyl coupling mechanism.     

Electrochemical deposition of poly(trans-[RuCl2(4-vinylpyridine)4]) and its reductive desorption: cyclic voltammetry and electrochemical quartz crystal microbalance studies

The electropolymerization of trans-[RuCl(2)(vpy)(4)](vpy = 4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry and the electrochemical quartz crystal microbalance (EQCM) technique. Cyclic voltammetry of the monomer in DMSO on Au shows reductions at -2.0 and -2.2 V. Potential cycling over the first wave leads to polymer formation; however, scanning over the second wave leads to desorption of the polymer. These observations were confirmed by EQCM measurements which also revealed a high polymerization efficiency. Electrolysis, EQCM and XPS measurements showed that desorption was associated with substitution of chloride ligands by DMSO when the polymer was in a highly reduced state. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. Measurements on the dried films revealed that large quantities of solvent are trapped in the film during the electropolymerization process.     

Bidimensional Spectroelectrochemistry Applied to the Electrosynthesis and Characterization of Conducting Polymers: Study of Poly[4,4′‐bis(butylthio)‐2,2′‐bithiophene]

The electropolymerization mechanism of 4,4′‐bis(butylthio)‐2,2′‐bithiophene ( 1 ) was studied by means of bidimensional spectroelectrochemistry. Simultaneous electrochemical and spectroscopic signals were analyzed with the aim of obtaining information about the role of the low‐molecular‐weight oligomers in the polymerization process. Experiments in electrochemical cells with finite (thin layer) and semi‐infinite diffusion geometries were carried out to elucidate the role the oligomeric species play, both in the nucleation step and in the subsequent growth of the polymer deposited onto the electrode surface.     

Electrochemically initiated chain polymerization of pyrrole in aqueous media

The electrochemical quartz crystal microbalance has been employed to investigate the electropolymerization of pyrrole in a variety of aqueous electrolytes. In contrast to the generally accepted cation–radical coupling process for the electropolymerization of pyrrole, an electrochemically initiated chain polymerization, featuring a high polymerization rate and involving little charge transport, was found under specific conditions in the presence of ClO^?₄, BF^?₄, and PF^?₆ electrolytes. The more typical cation-radical coupling mechanism, characterized by a constant polymerization charge to mass deposited ratio, is observed in the presence of Cl^?, NO^?₃, dodecyl sulfate, copper phthalocyanine tetrasulfonate, β-cyclodextrin tetradecasulfate, and poly(styrene sulfonate). Electrochemical characterizations of polypyrrole films prepared in aqueous ClO^?₄ electrolytes reveal that the polymer formed via chain polymerization exhibits the ability to transport both cations and anions during electrochemical switching between redox states, while the polymer synthesized through cation-radical coupling is only capable of transporting a single ionic species.     

Characterization of polybenzoxazine and its electrochemical polymerization mechanism

Poly(3-(p-methyl)benzyl-3,4-dihydro-6-methyl-2H-1,3-benzoxazine) (poly(pCpT)), which was obtained from electrochemical polymerization in acetonitrile/alkali aqueous solution, was characterized by FT-IR, UV-Vis and ¹H-NMR. The results indicate a ring-opening structure of the polymer. By using a rotating-ring disc electrode (RRDE), the electrochemical behaviors of polymerization were studied and the polymerization mechanism was proposed.     

导电聚合物的电化学制备和电化学性质研究——中国科学院有机固体重点实验室导电聚合物电化学研究工作简介(I)

简要介绍本研究组自上世纪80年代以来在导电聚合物的电化学制备和电化学性质研究中取得的一些主要成果,包括吡咯电化学聚合条件的影响、电化学聚合反应机理及其反应动力学、导电聚吡咯的两种掺杂结构及其两步电化学氧化还原过程和电化学过氧化的机理、导电聚苯胺的电化学性质、导电聚合物稳定性的电化学解释等等.     

Template-free one-step electrochemical formation of polypyrrole nanowire array

Oriented polypyrrole nanowire (nanorod) array readily forms using one-step pyrrole electropolymerization without using a template. These nanostructures having diameter in the range of 40–120 nm are obtained by electrogenerating polypyrrole in the presence of jointly non-acidic and weak-acidic anions. The latter are essential, their presence leads to the formation of an overoxidized polypyrrole thin layer that surrounds the polypyrrole nanostructure base. This simple and convenient method allows direct polymer nanowire array fabrication on various conductive substrates, the length of nanostructures being controlled by the polymerization time. Finally, a reaction mechanism involving oxidation of pyrrole and water and polypyrrole overoxidation is discussed.     

Redox mechanism and electrochemical behaviour or polyaniline deposits

Polyaniline (PANi) is prepared electrochemically by anodic oxidation of aniline in the eutectic mixture NH₄F, 2.35 HF (PANi-F), in aqueous sulfuric medium at different pH (PANi-S), or (PANi-N) if Na₂SO₄ is added. Thin deposits of PANi-F, prepared by potential step or sweeping, have a compact form at all aniline concentrations, with almost 100% polymerization yield and a strong adherence to the electrode. Thin deposits of PANi-N and PANi-S have identical characteristics, but only when prepared by potential sweeping at low aniline concentration. When the deposits are thick, only PANi-F displays these interesting properties, giving hard fibres, which adhere strongly to the electrode as the polymerization proceeds. Prepared with equal amounts of charge samples, a higher charge and discharge capacity is measured (coulombs) for PANi-F deposits than for PANi-N and PANi-S. Only PANi-F exhibits a faradaīc yield close to 1 after 2000 cycles.Observations on the electrochemical behaviour of PANi suggest a redox mechanism involving a proton + electron exchange and a doping process with ion insertion. The cyclic voltammograms obtained with PANi—coated electrodes show two or three rapid, reversible and clearly defined electrochemical systems. The second electrochemical system (2,2′) is obtained during the oxidation of aniline at higher potentials than those needed for the first (1,1′) and the third (3,3′) system. Therefore, a different structure of polymer may be associated with system 2,2′ than the para-coupling structure attributed to the systems 1,1′ and 3,3′. The polymerization of p-fluoraniline is possible (+0.72 V) at the same potential as aniline (+0.7 V). Hence, the participation of the ortho positions in the electropolymerization mechanism of aniline is a possibility to take into consideration. The cyclic voltammograms recorded during the electrodeposition of N-phenyl p-phenylenediamine, exhibit a similar form as those recorded for PANi-F. Therefore, it is confirmed that the polymerization of aniline proceeds through a head-to-tail coupling of cation radical.     

Elucidation of the electrochemical behavior of phenothiazine-based polyaromatic amines

Polyarlylamines with discrete redox active groups in the polymer backbone represent a promising class of cathode materials for electrical energy storage applications. In this area, our group recently reported a set of phenothiazine-based polymers that exhibit both high capacities and power densities. In order to rationally improve the properties of these electrode materials, a fundamental understanding of their electrochemical properties is indispensable. Herein, we probe the electrochemical behavior of our phenothiazine-based systems by synthesizing small molecule analogs using C–N cross-coupling. Additionally, electropolymerization of a class of these small molecule phenothiazines yields thin films that were then characterized with an electrochemical quartz crystal microbalance. Analysis of these materials provides insights into the number of electrons accessed from each repeat unit in our polymer backbone during electrochemical cycling, as well as counter ion transport dynamics.     

Polymers for electrochemical devices

Polymeric materials are already present in electrochemical storage devices such as batteries and PEM fuel cells. The polymer is an electro-active material in lithium polymer batteries. Several network based polymer electrolytes provide thermal, mechanical and redox stabilities, while insuring a high conductivity level. Linear unsaturated polyether precursors may be obtained either by step-growth polymerization from oligomeric polyethers, or by ring-opening polymerization from oxirane mixtures. Some prototype performances, performed on a 10 Wh lithium polymer cell, are presented and discussed.