砂磨法制备聚苯胺及其电化学性能的研究

首次采用砂磨法制备了导电态聚苯胺(PANI), 通过循环伏安和电导率的测试分析, 探讨了转速(N)、反应时间(t)、盐酸(HCl)浓度、十二烷基苯磺酸钠(SDBS)浓度和过硫酸铵(APS)浓度对产物氧化还原性及导电性能的影响|并采用红外光谱(FT-IR)对产物结构进行了表征. 结果表明: 当N为400 r/min, t为2 h, HCl与苯胺(An)的摩尔比(n_HCl/n_An)为4∶1, SDBS与An的摩尔比(n_SDBS/n_An)为1∶1, APS与An的物质的量比(n_APS/n_An)为0.8∶1时, 产物的各项性能达到最佳值|且砂磨法与乳液法制备的PANI结构相符, 电化学性能接近, 但是砂磨法的生产成本和环保优势十分显著(砂磨法的反应时间仅为乳液法的1/3, 用水量仅为乳液法的1/2).     

复合乳化剂微乳液法制备聚苯胺及其电化学性能

采用复合乳化剂微乳液法合成了导电聚苯胺(PANI),以碳纸负载PANI为工作电极,考察了十二烷基苯磺酸钠(SDBS)和聚乙二醇辛基苯基醚(TX-100)的配比及其复合乳化剂(E)和氧化剂(APS)用量对复合乳化剂微乳液法合成PANI电化学性能(循环伏安、塔费尔)的影响;通过对产物电导率和产率的对比分析,印证了PANI电化学性能表征结果的有效性。结果表明：当SDBS与TX-100的质量比为1/2,E与苯胺(An)单体的质量比为5/3,APS与An的摩尔比为1.2时,PANI的各项性能指标达到最好,且产物的循环伏安峰电流、腐蚀电位和电导率均高于单组分乳化剂SDBS或TX-100微乳液法制备的PANI。     

FeCl_3/APS复合氧化剂对乳液法合成聚苯胺动力学行为的影响

采用石英晶体微天平(QCM)技术,探讨了以三氯化铁(FeCl3)和过硫酸铵(APS)为复合氧化剂,十二烷基苯磺酸(DBSA)为乳化剂和掺杂剂时,苯胺(An)的乳液聚合动力学行为;并通过对产物的循环伏安分析,初步优化了聚合反应条件.结果表明,An的乳液聚合反应对复合氧化剂、An以及DBSA分别为1,0.5和0.5级.各种条件下的循环伏安(CV)图都显示出PAn的三对氧化还原特征峰.当FeCl3与APS物质的量比为2∶1;氧化剂总量与苯胺的物质的量比为3∶1;DBSA浓度为0.05mol/L时,CV测试的峰电流和电导率最大.     

APS/Fe2+复合氧化剂快速引发合成聚2,3-二甲基苯胺及其性能研究

采用乳液法,以过硫酸铵(APS)和硫酸亚铁(FeSO4)为复合氧化剂(COD),快速引发合成聚2,3-二甲基苯胺(P(2,3-DMA)).通过开路电位(OCP)、循环伏安(CV)和塔菲尔(Tafel)测试,探讨了Fe2+对2,3-DMA聚合速率的影响,优化了APS/Fe2+摩尔比(n(APS)/n(Fe2+))及COD用量.通过红外光谱(FTIR)和X-射线衍射(XRD)对比分析,印证了P(2,3-DMA)电化学性能的表征结果.结果显示,APS/Fe2+复合氧化剂引发合成的P(2,3-DMA),其FTIR的主要特征峰发生了红移,表明所得产物的结构更加完整,电子离域程度更大;当n(APS)/n(Fe2+)为10∶1,n(COD)/n(2,3-DMA)为3∶1时,产物的各项性能达到最佳;开路电位显示,Fe2+的加入使得2,3-DMA的聚合速率得到显著提高,采用复合氧化剂APS/Fe2+制备P(2,3-DMA)的产率增大,电化学性能和结晶性更佳.     

磁场对复配乳化剂/苯胺微乳液聚合体系相行为的影响

首次在酸性条件下, 以十二烷基苯磺酸钠(SDBS)和聚乙二醇辛基苯基醚(TX-100)为复配乳化剂, 制备SDBS/TX-100/正丁醇(nBA)/苯胺(An)/盐酸(HCl)微乳液体系, 并通过该体系的拟三元相图, 考察了恒定磁场(0.4 T)、助表面活性剂(nBA)与复配乳化剂的质量比(K_m＝m_nBA/m_SDBS/TX-100)及SDBS与TX-100的质量比(S_m＝m_SDBS/m_TX-100)对复配乳化剂/苯胺微乳液聚合体系相行为和电导行为的影响. 结果表明: 随着K_m的增加, 微乳区面积先增大后减小, 当K_m＝1.0时, 形成的微乳区面积最大|随着S_m的减少, 微乳区面积逐渐增大|外加磁场可以增大微乳区面积, 且随着S_m的减小, 磁场对微乳液体系的作用逐渐减弱. 循环伏安的测试结果表明, 复合乳化剂微乳液法制备的聚苯胺, 其循环伏安性能优于单组分乳化剂(SDBS或TX-100)微乳液法制备的聚苯胺.     

磁场对微乳液法合成聚苯胺结构及其电化学行为的影响

在不同磁场强度下,采用微乳液聚合法合成导电聚苯胺(PANI),以碳纸负载PANI为工作电极,通过循环伏安测试方法,探讨了磁场、氧化剂浓度和聚合时间对微乳液聚合法合成PANI电化学性能的影响;并通过X射线衍射(XRD)、四探针电导率测试和傅立叶红外光谱(FTIR)对产物结构和性能的表征分析,印证了循环伏安分析结果的可靠性.实验结果表明,与无磁条件下制备的PANI相比,磁场条件下制备的PANI具有较高的导电性和规整度;FTIR谱图分析表明,由于磁场的取向作用使分子间相互作用力降低,分子链离域程度增大,使磁场条件下合成PANI的主要特征峰有向低频方向移动的趋势,但分子的基本结构单元没有发生变化.研究结果显示,利用负载PANI的碳纸为工作电极,能够对微乳液法合成PANI的电化学行为进行有效的实时表征.     

聚苯胺的表面修饰及防腐性能

用八甲基环四硅氧烷(D₄)对聚苯胺(PANI)进行表面修饰, 通过对产物的循环伏安(CV)、 极化曲线(Tafel)以及接枝率的表征分析, 考察了反应温度、 反应时间、 单体用量和pH值对产物的接枝效果、 分散性和腐蚀电位的影响. 同时, 通过循环伏安(CV)、 紫外-可见光谱(UV-Vis)、 红外光谱(FTIR)、 X射线衍射分析(XRD)和热重分析(TGA), 对PANI表面修饰前后的结构和性能进行了比较. 结果表明, 通过D₄对PANI颗粒表面进行修饰, PANI的分散性、 分散稳定性和和防腐能力得到显著提高.     

脉冲电流法电解合成聚苯胺

在0.2mol/L苯胺和0.5mol/LH₂SO₄介质中采用脉冲电流法电解合成聚苯胺(PANI)膜.循环伏安研究表明,与恒电流法相比,脉冲电流法制得的PANI膜具有更好的电化学活性.扫描电镜(SEM)对膜层的微观形貌观察发现,这种特殊的聚苯胺膜层呈纳米纤维状结构,不同于恒电流法制取的颗粒状PANI膜.讨论了脉冲通断比和频率对于膜层性能的影响.     

有机化学接枝-电化学沉积聚合制备CNTs/PANI纳米复合材料

通过有机化学合成法先在碳纳米管表面接枝上苯胺单体,然后在不锈钢电极表面在硫酸溶液中采用循环伏安法电化学沉积聚合制得碳纳米管/聚苯胺(CNTs/PANI)纳米复合材料.扫描电子显微镜和傅立叶变换红外光谱表征所得材料的微观结构和基团,循环伏安和恒流充放电测试用于考察所得CNTs/PANI纳米复合材料的电化学性能.所得结果与...     

聚苯胺/铁氰化镍纳米复合颗粒的制备及电控分离Cd的EQCM研究

本文采用循环伏安一步共聚法在碳纳米管(CNTs)修饰的铂基底上制备了聚苯胺/铁氰化镍(PANI/NiHCF)纳米复合颗粒.通过电化学石英晶体微天平(EQCM)技术检测了复合颗粒制备过程的质量改变量,并用扫描电镜(SEM)、透射电镜(TEM)和傅立叶变换红外光谱(FTIR)分析了复合颗粒的微观形貌和组成.结合循环伏安法和EDS能谱考察了该复合电极对Cd2+离子的交换性能.结果表明,三维多孔的CNTs不仅可促进复合颗粒的沉积,而且其独特的网络结构和表面特性对形成PANI/NiHCF复合颗粒的立方体构型起至关重要的作用.该复合电极在0.1mol·L-1Cd(NO3)2溶液中显示了良好的电活性,对Cd2+离子有可逆的离子交换性能,通过电控离子交换法可实现废水中Cd2+离子的高效分离.     

Surfactant-assisted synthesis of polyaniline nanofibres without shaking and stirring: effect of conditions on morphology and conductivity

Polyaniline (PANI) nanofibres were synthesised by the chemical oxidative polymerisation method using ammonium peroxydisulphate (APS) as an oxidant/initiator. In this work, a surfactant-assisted method without shaking and stirring was used for the synthesis of PANI nanofibres. The effect was investigated of various parameters such as monomer/oxidant ratio, polymerisation temperature, and the presence of surfactant (Triton X-100 as a non-ionic surfactant) on the morphology and electrical conductivity of nanofibres. The morphology of PANI nanofibres was characterised by scanning electron microscopy and transmission electron microscopy. The results demonstrate that the morphology of PANI nanofibres was significantly influenced by the aniline/APS mole ratio, polymerisation temperature and presence of the surfactant during synthesis. The results showed that more regular and consistent nanofibres were obtained using a monomer/oxidant ratio of 4 at ambient temperature of polymerisation. PANI nanofibres with diameters in the range of 10?C100 nm and length up to several ??m were obtained. PANI nanofibres were also characterised using FTIR and UV-VIS absorption spectroscopy. The electrochemical behaviour of PANI nanofibres was studied by cyclic voltammetry. It was found that the electrical conductivity of PANI nanofibres increased with the increasing monomer/oxidant ratio and decreasing polymerisation temperature, respectively.     

以含有阿魏酸和没食子酸的PAM纤维诱导制备聚苯胺纳米棒结构材料

为了研究化感物质的缓释载体材料, 分别以含有阿魏酸和没食子酸的聚丙烯酰胺(PAM)纤维诱导, 采用化学氧化聚合法, 以苯胺为单体, 过硫酸铵为氧化剂, 分别合成了阿魏酸、没食子酸掺杂的聚苯胺(PANI)纳米结构材料. 通过红外光谱(IR)、X射线粉末衍射(XRD)以及电子扫描电镜(SEM)对掺杂态PANI的结构和形态进行了表征. 结果表明, 所制备材料确为阿魏酸、没食子酸掺杂的PANI. SEM研究结果表明, PANI的形态表现为纳米棒状, 直径在200~300 nm范围内. 另外, 对纤维中酸含量以及不同氧化剂和苯胺单体摩尔比对PANI电导率的影响进行了探讨.     

氯化铁氧化掺杂的聚苯胺纳米纤维团簇

没有外加质子酸的条件下,以氯化铁为氧化剂和掺杂剂,在界面体系中由苯胺(An)采用“无模板”的方法成功地制备了电导率为10-2～10-1S/cm的聚苯胺纳米纤维(d=20～30nm).实验证明FeCl3同时起到氧化剂和掺杂剂的双重作用,从而进一步简化了导电聚苯胺纳米纤维的合成条件.与使用过硫酸铵为氧化剂的传统聚合方法相比,FeCl3较小的氧化/还原电位使产物具有较小的直径和较高的结晶性.同时发现聚苯胺的形貌和电导率均与[FeCl3]/[An]的比例有关.FTIR,UV-Vis,XRD结构表征证实所得的聚苯胺纳米纤维为掺杂态.     

一步法合成聚苯胺/十二烷基苯磺酸钠超疏水复合材料

在阴离子表面活性剂十二烷基苯磺酸钠(SDBS)体系中,采用一步法制得聚苯胺/SDBS超疏水复合材料.利用场发射扫描电子显微镜(FESEM)观察产物形貌并测定其元素组成.通过傅里叶变换红外光谱仪、紫外-可见光谱仪、X射线衍射等对其结构进行表征,用视频接触角测量仪测定材料的亲疏水性.考察SDBS浓度和溶液酸度对产物形貌及疏水性能的影响,探讨疏水机理.结果表明:在pH=1-9,SDBS浓度大于0.016 mol?L-1条件下,所制备复合材料的水接触角大于150°,SDBS掺杂使得苯胺单体的转化率高达98%.两亲分子SDBS亲水磺酸基与聚苯胺主链上的亚胺基不仅存在静电引力,而且能形成磺酰胺键,聚苯胺主链间又以氢键相互连接,SDBS分子的疏水烃基有序排列朝向聚苯胺主链外侧,从而组装形成具有微纳结构的聚苯胺/SDBS超疏水复合材料.本文结果有利于更好地理解聚苯胺/SDBS超疏水性复合材料的形成机理,对超疏水材料的设计提供新思路.     

Inkjet printable polyaniline nanoformulations

Aqueous polyaniline (PANI) nanodispersions doped with dodecylbenzenesulfonic acid (DBSA) were synthesized and successfully inkjet-printed using a piezoelectric desktop printer. This paper examines the optimization and characterization of the nanoparticulate formulation for optimal film electrochemistry and stability. PANI nanoparticle synthesis was optimized in terms of the ratio of monomer (aniline) to oxidant (ammonium persulphate, APS) and dopant (DBSA). Particle size, UV-vis spectroscopy, electrochemical, and conductivity analyses were performed on all materials. Optimal synthesis conditions were found to be at a molar ratio of 1.0:0.5:1.2 aniline/APS/DBSA. This resulting nanodispersion showed a uniform particle size distribution of approximately 82 nm, and UV-vis analysis indicated a high doping level. These synthetic conditions resulted in the highest conductivity, and the electrochemistry of the resulting films was well-defined and stable. Surface tension analysis and rheological studies demonstrated that the aqueous nanodispersions were suitable for inkjet printing. Successful inkjet printing of these polyaniline nanoparticulate formulations is demonstrated.     

Synthesis of PANI and Study of Morphology in the Process of Polymerization

The polyaniline micro/nanostructure was prepared by a self‐assembly process with molybdic acid as dopants in the presence of ammonium persulfate as the oxidant. It was found that the morphology of PANI micro/nanostructure was affected by the concentration of the dopant, that is, the morphology of PANI changed from nanofibers to co‐existence of nanofibers and microspheres as the molar ratio of molybdic acid to aniline varied from 0.01 to 1.5. Under the same condition it was also found that the conductivity value of PANI enhanced from 4.58×10^?3 S·cm^?1 to 3.8×10^?1 S·cm^?1. The structure of PANI was characterized by FTIR and XRD which confirmed the presence of the molybdic acid in the PANI. The electrochemical characteristics of the PANI nanofibers were investigated by means of cyclic voltammetry. The morphology of PANI in the process of polymerization was characterized by SEM. It was found that when the molar ratio of molybdic acid to aniline was 0.3, the morphology of PANI was co‐existence of nanofibers and microspheres and the formation of microspheres was ahead of the nanofibers.     

Synthesis of Poly(3,4-ethylenedioxythiophene) Hollow Spheres in CTAB/DBS — Mixed Surfactant Solutions

Summary: Hollow microspheres of PEDOT (poly(3,4-ethylenedioxythiophene) ranging from 0.5 to 10 µm have been synthesized by chemically oxidative polymerization of EDOT(3,4-ethylenedioxythiophene) using ammonium persulfate in a catanionic surfactant solution obtained by mixing cetyltrimethylammonium bromide (CTAB) and sodium dodecylbenzenesulfonate (SDBS). The effect of the molar ratio of CTAB to SDBS on the morphology of the PEDOT oxidation products has been investigated using SEM and TEM and by an analysis of the structural properties using UV-visible, FTIR and Raman spectroscopies, elemental analysis and conductivity measurements. The electro-catalytic activity of PEDOT hollow microspheres for the oxidation of ascorbic acid was investigated by cyclic voltammetry in a pH 6 citrate/phosphate buffer solution and compared to the activity of granular PEDOT particles formed in the absence of the catanionic surfactant.