电化学制备有序聚苯胺纳米线阵列

以有序碳纳米管阵列电极为基底电极,在硫酸或高氯酸溶液中,分别探明不同电化学聚合方法以及苯胺单体浓度对聚苯胺形貌的影响. 结果表明：采用循环伏安法无法制备出聚苯胺纳米线;而应用恒电位法虽可制得聚苯胺纳米线,但纳米线不能形成有序阵列;只有应用恒电流方法,并且以高浓度苯胺的高氯酸溶液作为聚合溶液,方能制得有序聚苯胺纳米线阵列.     

聚吡咯纳米阵列电极的光电化学

以多孔的铝阳极氧化膜(AAO)为模板制备了直径约为80 nm聚吡咯(PPy)纳米线的阵列电极, 并研究了它的光电化学响应. 结果表明, 在电极电位低于－0.1 V(vs Ag/AgCl)时出现的阴极光电流是由聚吡咯纳米线的p型半导体性质引起的, 其平带电位为－0.217 V. 聚吡咯纳米线的长度对光电流的影响较大, 最佳长度为42 nm. 这是因为在很短的聚吡咯纳米线阵列中PPy太少, 产生的光电流弱, 而在过长的聚吡咯纳米线阵列中光生电子在到达电极基底前易于与光生空穴复合而消失. 聚吡咯纳米线有可能作为纳米光电器件用于未来微器件系统.     

吡咯聚合调控脉冲电沉积制备球形羟基磷灰石和银纳米粒子复合涂层

借助聚吡咯(PPy)的调控,采用脉冲电沉积法在生物医用金属钛表面制备出均匀的纳米HA/PPy/Ag抗菌复合涂层.考察了电解液中Py浓度、Ag~+浓度、钙磷盐浓度等对复合涂层的形貌及成分的影响.探讨了PPy聚合过程形成球形HA-NPs和Ag-NPs的形成机理,并对复合涂层的生物活性、生理稳定性及抗菌性能进行研究.研究结果表明,电解液中Py浓度的高低影响涂层的形貌,Py浓度为0.03 mol/L时有利于复合涂层的沉积.电解液中Ag~+浓度影响涂层的形貌、结晶,电解液中Ag~+浓度为0.3 mmol/L左右比较适合.电解液中Ca~(2+)浓度影响涂层的形貌及结晶,其浓度过高颗粒尺寸增大,Ca~(2+)浓度为5.0 mmol/L左右较适合.复合涂层能够诱导磷灰石的生成,使其沿着(002)晶面出现择优生长,具有较好的生物活性.PPy的加入大大降低了复合涂层中Ca~(2+)和Ag~+的释放速度,提高了复合涂层的生理稳定性.抗菌检测表明复合涂层具有良好的抗菌性.     

用离子吸附法制备银/聚吡咯同轴纳米电缆

以多元醇还原反应法制备出直径为40~50 nm的纳米银线, 采用醋酸铜水溶液对银纳米线表面进行处理, 通过离子吸附在纳米银线表面吸附铜离子. 以吸附在银纳米线表面上的铜离子作为活性单元, 氧化吡咯单体聚合, 制得Ag/PPy同轴纳米电缆. 采用TEM, FTIR和XPS等表征手段对产物进行表征和检测, 并通过表面增强拉曼光谱进一步证实产物中聚吡咯层紧密地吸附在银线表面. 结果表明, 利用醋酸铜作为氧化剂, 通过离子吸附法制备的Ag/PPy同轴纳米电缆, 可以在较大范围内有效地控制聚吡咯层厚度, 避免银纳米线被刻蚀.     

无纺布基聚吡咯柔性电极的储锂性能

高性能的柔性锂离子电池对可穿戴电子设备的发展具有重要意义。采用化学氧化法在聚对苯二甲酸乙二醇酯(PET)无纺布基材上原位聚合聚吡咯(PPy),并通过控制反应条件得到不同形貌的聚吡咯电极材料。当反应体系中剪切力较小时,得到纳米线状聚吡咯(PPy-NW/PET),反之,为纳米颗粒形貌的聚吡咯(PPy-NP/PET)。PPy纳米线的平均直径为460 nm,在包覆PET纤维的同时相互交叠,形成了三维网状导电通道。该PPy/PET可以直接作为无粘结剂的柔性电极材料。电化学测试结果表明,PPy-NW/PET电极材料的性能更优异,其首次放电和充电的比容量分别为124和98 mA[DK1]·h/g,且具有良好的柔性和稳定性。本文对柔性、轻质电极材料的制备及其在储能领域的应用提供了很好的思路。     

不同状态下聚吡咯膜的电化学阻抗

用恒电流法分别聚合了掺杂对甲苯磺酸根(pTS-)和十二烷基磺酸根(DS-)的聚吡咯膜(PPy/pTS和PPy/DS),通过循环伏安法(CV)和电化学阻抗法(EIS)测试了聚吡咯膜在NaCl溶液中‘过电位’电化学过程前后及不同电位下聚吡咯膜的电化学性能.同时,通过嵌入和脱出Na+和Cl-离子的聚吡咯膜在特定溶液中电化学阻抗图谱,研究了离子的嵌入对聚吡咯膜电化学性能的影响.结果表明‘过电位’现象可以提高聚吡咯膜的离子电导率和膜电容,Cl-离子的嵌入能提高PPy/pTS的电导率,而Na+离子的嵌入对聚吡咯膜的电导率影响不大.另外,嵌入离子对聚吡咯膜形貌的改变会对聚吡咯膜的离子传导率有一定影响,从而导致膜的电化学阻抗的变化.     

基于静电吸附作用制备PPy/CNTs复合材料

通过添加十二烷基苯磺酸钠(SDBS), 在碳纳米管(CNTs)表面引入具有静电吸附作用的基团, 使吡咯单体附着于CNTs表面, 然后发生化学原位聚合, 得到了由片状聚吡咯(PPy)包覆CNTs所构成的PPy/CNTs复合材料, 开辟了一条易于工业化生产制备PPy/CNTs复合材料的途径. 所得材料和CNTs借助傅立叶变换红外光谱、扫描电子显微镜、透射电子显微镜等设备进行了成分和形貌的表征; 并将所得材料组装成电化学超级电容器, 进行了电化学性能测试. 研究结果表明, 加入SDBS后, 吡咯单体能很好地吸附于CNTs表面; CNTs的应用细化了PPy的颗粒, 改善了PPy的导电性能和机械性能, 使PPy/CNTs复合材料呈现出多孔状; 其电化学容量达到101.1 F·g-1(有机电解液), 是同样制备条件下所得纯PPy电化学容量(19.0 F·g-1)的5倍多, 约是所用纯CNTs电化学容量(25.0 F·g-1)的4倍.     

聚吡咯纳米球负载金纳米粒子的制备及其性能研究

在水溶液中以表面活性剂F127形成的胶束为模板制备聚吡咯纳米球，考察了温度、吡咯浓度、pH等因素对聚吡咯纳米球形貌的影响，提出F127体系中聚吡咯纳米球的形成机理。利用聚吡咯与氯金酸之间的氧化还原活性，在聚吡咯纳米球表面成功负载金纳米粒子，研究温度和吡咯浓度对聚吡咯/金复合材料形貌的影响，运用透射电子显微镜、傅里叶红外光谱、X射线衍射、拉曼光谱、循环伏安等对其形貌、结构、性能进行研究。结果表明，所制得的负载金纳米粒子的聚吡咯复合材料具有明显的拉曼增强效应，可用于分析复合材料中聚合物的分子结构；此外该复合材料在酸性条件下具有较好的电化学稳定性，可应用于修饰电极。     

不同形貌聚吡咯及其复合材料的合成与电化学应用研究进展

聚吡咯(PPy)具有良好的电荷传输能力,PPy与金属氧化物、硫化物复合材料具有优异的电化学性能。本文综述了硬模板、软模板存在下纤维状、管状、球状等不同形貌PPy的制备,PPy与单金属/双金属氧化物、硫化物可构筑纤维状、管状、球状等不同形貌的复合材料,着重介绍了化学氧化聚合法制备不同形貌的PPy及其复合材料。本文还概述了不同形貌的PPy及其与金属氧化物、硫化物复合材料在超级电容器、锂离子电池、传感器等电化学领域的应用。     

不同形貌聚吡咯的制备及其电化学性能研究

以吡咯为单体,用化学氧化法和电化学沉积法分别制备聚吡咯(PPy)纳米粒子和微球。实验表明,PPy-ED微球的比电容要优于PPy-CS纳米粒子,并且PPy微球表现出理想的赝电容行为,可以进行快速可逆的法拉第反应,其原因在于PPy微球分子链规整,具有较大的共轭程度,从而表现出优异的电化学储能性。     

聚吡咯/硫化镉核壳纳米线的制备及整流特性

以无机多孔氧化铝膜为模板,利用气相沉积和原位电化学沉积方法成功地制备了有机-无机杂化聚吡咯/硫化镉核壳纳米线;采用扫描电子显微镜和透射电子显微镜分析了聚吡咯/硫化镉核壳纳米线的表面形貌和微结构.结果表明,内部的聚吡咯纳米线紧紧依附在外部的硫化镉纳米管中,并且硫化镉纳米管被聚吡咯全部填充.与此同时,在聚吡咯/硫化镉核壳纳米线中,外部硫化镉壳与内部聚吡咯核之间存在电荷转移;聚吡咯和硫化镉之间形成有机-无机杂化的P-N界面,从而导致单根聚吡咯/硫化镉核壳纳米线显示出不同于外部壳和内部核的整流特性.     

ZnO/PPy异质纳米复合材料的制备、表征及其气敏特性

室温下, 采用原位聚合法, 以吡咯(PY)为单体, 氯化铁(FeCl₃·6H₂O)为氧化剂, 在塑料基片上聚合生长了聚吡咯(PPy)纳米微球. 然后在聚吡咯基片上生长ZnO种子, 将表面种有ZnO种子的PPy元件置于六次甲基四胺与硝酸锌的混合溶液中, 90 ℃水浴中, 在PPy微球上生长了ZnO纳米棒, 合成了PPy/ZnO异质纳米复合材料. 分别通过X射线衍射仪(XRD)和场发射扫描电镜(FESEM)对PPy/ZnO异质纳米复合材料的结构和形貌进行了表征. 制备了塑料基的PPy/ZnO异质纳米复合材料气体传感器, 在室温下, 对10×10^-6-150×10^-6 (体积分数)浓度范围的氨气进行了气敏测试, PPy/ZnO气敏元件对氨气响应的灵敏度基本呈线性关系, 且对甲醇、丙酮、甲苯等有机气体表现出很好的选择性. 最后, 对PPy/ZnO异质纳米复合材料的形成机理进行了简要分析.     

Polypyrrole (PPy) chemical synthesis with xylan in aqueous medium and production of highly conducting PPy/nanofibrillated cellulose films and coatings

Polypyrrole was chemically synthesised by using, for the first time, Birchwood xylan as additive, and ammonium peroxydisulfate (APS) as oxidant. The impact of additive concentration, polymerisation time and reagents concentration on PPy conductivity was studied. It was shown that, once fixed the pyrrole (Py)/APS and Py/xylan optimal ratios, the best conductivities (26 S/cm) were obtained for short polymerisation times (30 min) and increased reactants concentration. Morphological analysis of PPy particles, Py depletion kinetics and oxido-reduction potential measurements of the solutions provided interpretation elements on the impact of the polymerisation time on PPy pellet conductivity. Furthermore, optimised PPy particles obtained with xylan (PPy_x) were mixed with nanofibrillated cellulose (NFC) in order to obtain freestanding films. Their electrical and handling performances were evaluated at increasing PPy weight fraction in the samples. The conductivity mechanism of the most conductive sample (in comparison with a low performing sample) was investigated by measuring the conductivity as a function of temperature (4–350 K) and two transport regimes were identified. Selected formulations were finally used to produce conducting PPy/NFC coatings on non-absorbent (glass) and absorbent (copy paper) substrates. The impact of NFC in the percolation of PPy particles, then in the coating conductivity, was investigated.     

聚吡咯/多壁碳纳米管及其聚氨酯导电复合材料的制备和性能

以羧基化多壁碳纳米管(MWCNTs)做模版剂,采用化学氧化法将吡咯(Py)在羧基化MWCNTs表面聚合制备PPy/MWCNTs导电材料,将其添加到溶剂型聚氨酯(PU)溶液中制备了PPy/MWCNTs/PU导电复合材料,研究了Py用量对PPy/MWCNTs及其PU复合材料性能的影响.研究表明,随Py用量的增加,PPy/MWCNTs的长度不变,管径增大,sp~2和sp~3杂化C含量先提高后减少,N的掺杂梯度降低,PPy/MWCNTs的导电率高于羧基化MWCNTs和PPy.当Py用量为羧基化MWCNTs的20%时,其导电率最大.PPy/MWCNTs中N元素的掺杂程度及其管径变化是引起PPy/MWCNTs/PU复合材料的性能不同的主要原因.增加Py用量,MWCNTs中亲水的羧基因对PPy掺杂而消耗,相同导电材料用量时纳米导电粒子数目相对减少,PPy/MWCNTs/PU复合材料的耐水性能提高,定向应力、储能模量和玻璃化温度降低,导电率先增加后减小.当Py用量为羧基化MWCNTs的15%时,导电率最大.     

聚ε-己内酯/聚吡咯电纺膜的制备与性能

以吡咯(Py)和聚ε-己内酯(PCL)为原料、氯仿为溶剂,并掺杂一定量的十二烷基硫酸钠制备电纺膜,利用三氯化铁的氧化作用原位生成聚吡咯(PPy).对所得到的PCL/PPy电纺膜用红外光谱进行表征,在扫描电镜和透射电镜下观察纤维形貌,并测定力学性能和体积电阻率.结果表明,所生成的PPy以纳米粒子形式附着在电纺纤维表面,随着Py相对于PCL的质量百分含量由0增加到20%,PCL/PPy电纺膜的纤维直径从(730±341)nm逐渐下降至(325±84)nm;膜的拉伸模量和拉伸强度由不含Py的(25.7±0.8)MPa和(2.48±0.14)MPa分别增加至含有20%Py的(48.4±7.6)MPa和(5.05±0.59)MPa,断裂伸长率由(129±27)%下降至(86.2±9.1)%;体积电阻率降低了2～3个数量级.该PCL/PPy电纺纤维膜以期可作为电活性材料用于功能或生物医用领域.     

Preparation of NiAl double hydroxide@polypyrrole materials for high‐performance supercapacitors

A novel NiAl double hydroxide@polypyrrole (LDH@PPy) core–shell material was designed and fabricated by a facile in situ oxidative polymerization of pyrrole (Py) monomer. The microstructure and morphology of the LDH@PPy composites were determined by X‐ray diffractometer, Fourier transform infrared (FTIR), scanning electron microscopy/transmission electron microscopy, and thermogravimetric and differential thermal, revealing that the polypyrrole (PPy) was successfully coated onto the surface of the NiAl‐LDH (LDH) core and the loading amount of PPy impacted the thickness and the dispersion of the conductive PPy shell. The electrochemical performances of the LDH@PPy composites were also evaluated by cyclic voltammogram, electrochemical impedance spectroscopy, and galvanostatic charge–discharge measurements. The results indicated that the supercapacitor performances were attributed to the synergy of unique core–shell heterostructure and each individual component, where the LDH core provided the high‐energy storage capacity and the PPy shell with networks had high electronic conductivity. These shorted the ion diffusion pathway and made electrolyte ions more easily accessible for faradic reactions to enhance the electrochemical performance of the LDH@PPy composites. It was found that the LDH@PPy composite (LDH@PPy₇) fabricated at 7 mL?L^?1 of Py monomer feed exhibiting the best electrochemical performances with high specific capacitance of 437.5 F?g^?1 at 2 A?g^?1 and excellent capacitance retention of about 91% after 1000 cycles. The work provides a simple approach for designing organic–inorganic core–shell materials with potential application in supercapacitors. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1653–1662     

Preparation of polypyrrole‐graft‐poly(N‐isopropylacrylamide)/silver nanocomposites from pyrrolyl‐capped macromonomer by AgNO3 and their stimuli responsibility of light emission

Pyrrolyl‐capped poly(N‐isopropylacrylamide) macromonomers (Py‐PNIPAM) were prepared through reversible addition‐fragmentation‐transfer polymerization with benzyl 1‐pyrrolylcarbodithioate as chain‐transfer agent. Polymerizations of Py‐PNIPAM with/without pyrrole using AgNO₃ as oxidizing agent and dimethylforamide as solvent resulted in graft copolymers of polypyrrole‐graft‐poly(N‐isopropylacrylamide) (PPy‐g‐PNIPAM) as well as silver nanoparticles, leading to the formation of PPy‐g‐PNIPAM/silver nanocomposites. The resulting nanocomposites were soluble in water when the content of PPy was low, and when the molar ratio of Py/Py‐PNIPAM increased to 30, the resulting products became insoluble in water. The resulting nanocomposites had special optical properties because of PPy as well as the temperature‐responsible PNIPAM. The chemical structure and composition of nanocomposite were characterized by ¹H nuclear magnetic resonance spectroscopy, gel permeation chromatograms, fourier transform infrared spectroscopy, and X‐ray diffraction. Their optical properties were characterized by UV–vis and fluorescence spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6950–6960, 2008     

Heparin‐Controlled Growth of Polypyrrole Nanowires

Summary: Heparin, a potent anticoagulant, has been used for the first time for the synthesis of PPy nanowires serving not only as an anion dopant but also as an effective morphology‐directing agent. The obtained PPy nanowires exhibit long and fine structures with smooth surface and the average diameter of the nanowires is about 90–100 nm and lengths are several hundred nanometers to micrometers. The possible formation mechanism of PPy nanowires may be related to the chain structure of heparin with functional groups ( SO and  COO⁻) on the surface. The effect of concentrations of pyrrole monomers and heparin on the morphology and size of PPy nanowires has been investigated.

SEM image of PPy nanowires synthesized in the presence of heparin.     

聚吡咯/还原氧化石墨烯复合物的合成及电容性能

通过原位聚合方法制备不同配比的聚吡咯/氧化石墨（PPy/GO）复合物,将其用NaBH4还原得到聚吡咯/还原氧化石墨烯(PPy/RGO)复合物,采用X射线衍射、红外光谱和场发射扫描电子显微镜（FESEM）对其结构和形貌进行物理表征。 采用循环伏安、恒电流充放电和交流阻抗等电化学方法系统研究了所制备样品的电化学性能。 实验结果表明,在电流密度为0.5 A/g、吡咯（Py）与GO质量比为95∶5时,得到的复合物还原前后比电容分别可达401.5和314.5 F/g,远高于单纯的GO（34.8 F/g）和PPy（267.5 F/g）。 经过1200圈循环稳定性测试后,PPy/RGO复合物比电容保持了原来的62.5%,与PPy和PPy/GO（电容保持率分别为16.8%和46.4%）相比,PPy/RGO表现出更好的循环稳定性能,有望成为超级电容器电极材料。     

Polyamide grafted with polypyrrole: formation, properties, and stability

Conducting textiles of polyamide (PA) fabrics and polypyrrole (PPy) were prepared by in situ oxidative chemical polymerisation of pyrrole (Py) on the surface of PA textiles using FeCl₃ as oxidant. The anionic surfactant, dodecylbenzenesulphonic acid, was used as co-dopant during Py polymerisation on the textile surface. The influence of the monomer amount and polymerisation conditions on formation of the conducting PPy layer, conductivity, morphology, and stability of the prepared PA/PPy was studied. The conductivity of modified textiles decreased rapidly after the washing process, so a special Py-functionalised silane (1-(3-(triethoxysilyl)propylamino)-3-(1-H-pyrrole-1-yl)propan-2-ol; SP) was synthesised and applied to the PA surface prior to PPy formation. The presence of SP on the PA surface after completion of the sol-gel process was verified by Fourier transform infrared spectroscopy with an attenuated total reflectance. Pyrrole polymerisation was subsequently applied to the SP pre-treated textile surface. The influence of SP concentration on both the fastness of the conducting layer after the washing process and stability of the electrical conductivity of the prepared PA/PPy samples was investigated. Surface conductivity of the samples treated and untreated by the sol-gel process of SP was measured both prior to and after washing of the prepared textiles. It was found that an application of 0.6 mass % of SP significantly improved the fastness of the PPy layers. Examination of the modified PA surface using scanning electron microscopy disclosed the differences in the formation of PPy on PA textiles when using SP and also showed differences on the PPy modified textile surface prior to and after washing. The method of X-ray photoelectron spectroscopy was used for a detailed study of the surface composition. It was confirmed that the pre-treatment with Py-functionalised triethoxysilane significantly influenced the chemical composition of the PA surface modified with PPy.