Self-assembly of Polyaniline: Mechanism Study

Anisotropic polyaniline (PAni) plates decorated with self-aligned nanofiber arrays were synthesized under the hydrothermal conditions. The formation mechanism of the self-assembled structures was investigated by studying the effect on PAni micro-structure with additive electrolyte in reaction system, and numerical simulation for dependence of systematic electrostatic energy on cross angles of self-assembled nanofiber arrays in grid textured PAni plates. It is proposed that the electrostatic interaction based on ionic doping charges plays an important role in the formation of the self-assembled PAni structures.     

溶液中光诱导产生岩藻黄质自由基正离子的动力学机制

对比研究了岩藻黄质(Fuc)在氯仿和甲醇溶液中光诱导生成自由基正离子(Fuc·+)的动力学过程,考察了2种不同溶剂中Fuc·+产生机制的差异.采用光谱电化学方法结合纳秒时间分辨吸收光谱技术,通过比较直接光激发和三重态敏化2种不同方式诱导生成Fuc·+的动力学过程发现,在氯仿溶液中Fuc·+主要源于Fuc的单重激发态(S2),在甲醇溶液中则主要源于Fuc的三重激发态(T1).     

O/W微乳液中聚苯胺超微粒子的制备

选择合适的ＳＤＢＳ／苯胺／Ｈ２Ｏ三组分Ｏ／２微乳液与苯胺单体共存的两相体系，以单体相为单体源，在Ｏ／Ｗ厂组分微乳液中进行了苯胺聚合，所得聚苯胺粒子大小仅为３ｍ，分布较均匀，且具有较好的导电性能。     

Efficacy of Polyaniline (PANI) nanofibres for capturing Diclofenac (DC) drug from its aqueous solutions

Pharmaceutical drug contamination in water nowadays is deteriorating the ecological components. A remedial approach is therefore a necessity. This study focuses on the synthesis of PANI nanofibres employing the oxidative polymerization method using ammonium persulphate (APS) as oxidant. The synthesized nanofibres were characterized using HR-TEM, FT-IR and XRD. The HRTEM image exhibited the nano-range structure of PANI with a rough surface. The FT-IR spectra inferred about the role of surface capping groups involved in the uptake mechanism. The crystallinity of PANI was well assessed by the X-Ray Diffraction analysis. The interaction between the studied drug diclofenac (DC) and polyaniline (PANI) showed a rapid equilibrium time 120 min favored at pH 5.0 achieving maximum adsorptive capacity (q_e) of 471.08 mg g ^?1. The uptake process followed the pseudo-second order kinetic model (R² = 1) with intra-particle diffusivity model (R² = 0.9810) as the governing step and best fitting values into Langmuir isotherm model (R² = 0.9822) inferred about the favourable adsorption of DC forming monolayer over PANI having q_m to be 943.83 mg g^?1. The drug DC was easily desorbed up to 85.31% by using 0.1 M aq ethanol and was exhausted after five cycles of reusability. The whole adsorptive mechanism involved electrostatic interactions along with hydrogen bonding.     

Polyaniline composites: improving the electrochemical properties by template synthesis

We have been exploring the idea of using the heterogeneous porosity of inorganic (sol-gel silica) and organic (poly(vinylidene fluoride)) films as a template for the preparation of polyaniline composites. The large size pore distribution (~2.5–800 nm) in both template matrices results in a part of the polyaniline growing more ordered than in films synthesized without spatial restriction. Small-angle X-ray scattering and scanning electron microscopy experiments were done to determine the extreme values of the pore diameters. Using other experimental techniques, including cyclic voltammetry, UV-Vis-NIR spectroscopy, electrochemical impedance and chronopotentiometry, we concluded that the electrochemical properties of polyaniline, such as oxidation and reduction charges, diffusion coefficient and charge-discharge capacity, are improved in these composites. Electronic Publication     

环硅氧烷开环聚合反应的机理及动力学研究

环硅氧烷在亲核或亲电催化剂、温度或辐射作用下,可开环聚合生成线型聚硅氧烷,聚合方法主要有本体聚合和乳液聚合.本体聚合可分为阴离子聚合和阳离子聚合,阴离子聚合就是在碱性催化剂(亲核试剂)作用下,使环硅氧烷开环聚合成线型聚硅氧烷的过程;阳离子聚合就是环硅氧烷在酸性催化剂(亲电试剂)作用下的开环聚合反应.乳液聚合则是单体和水(或其它分散介质)并用乳化剂配成乳液状态进行聚合,按所采用的乳化剂种类不同,主要有阴离子型和阳离子型两种类型.本文总结了近几年国内外环硅氧烷本体聚合和乳液聚合的开环聚合机理及动力学研究情况,并对今后此方面的研究进行了展望.     

Kinetics and Mechanism of Radical Polymerization

Low molecular reactions are frequently accompanied by side reactions producing a whole spectrum of by-products whose removal in purification operations generally causes little difficulty because the major and side products usually differ sufficiently in their properties. Hence detailed kinetic studies in low molecular chemistry can claim industrial interest only insofar as they aim to reduce the rate of formation of side products. The situation is completely different in polymer chemistry, where the terms major and side product no longer apply. Instead, one obtains mixtures of similar and/or isomeric molecules which differ so little with regard to molecular weight and structure that resolution into pure substances or isolation of pure substances becomes practically impossible. However, since all partial reactions exert a direct influence on the product spread, i.e. the composition and properties of a product mixture are modified by any change in operating conditions, detailed kinetic analyses embracing all relevant partial reactions are an essential prerequisite for the production of defined polymeric products on any scale. This progress report illustrates the importance of kinetics for radical polymerization with the aid of selected examples.     

In-Situ Electron Spin Resonance Studies of Polyaniline

In-situ electron spin resonance studies of polyaniline at various applied potentials in media of pH 0.49, 2.09, 3.96, anf 9 are reported. The g factor of the esr signal is 2.0036 and does not vary with the applied potential. The peak to peak linewidth decreases to a minimum in a potential range which depends on the pH of the medium. On the other hand, the spin density increases to a maximum in the same potential range. The pH-potential range where the highly conductive form exists, matches very well the range of narrow linewidth and high spin density of the esr signal. The conductive form of polyaniline consists of highly mobile radical cations or polarons.     

聚合时间对染料敏化太阳能电池中聚苯胺对电极结构和性能的影响

采用恒电压方法, 以掺杂氟的SnO₂ (FTO)导电玻璃为基底, 采用不同的聚合时间制备SO₄^2?掺杂的聚苯胺对电极(PANI CEs). 利用扫描电子显微镜(SEM)、紫外-可见(UV-Vis)吸收光谱、循环伏安法(CV)和电化学阻抗谱(EIS)等技术详细研究了聚合时间对PANI CEs的表面形貌、结构(如掺杂度、共轭性、氧化态等)和对I^?/I^3?的催化活性的影响. SEM结果表明PANI在FTO上的生长分两个阶段. 适当增加聚合时间可以增加PANI CEs的比表面积, 为催化I^?/I^3?反应提供更多的活性位点, 同时聚苯胺链的共轭性、半氧化态聚苯胺(EB)结构的含量和对阴离子SO₄^2?的掺杂度会随着增加, 进而PANI 的导电率也逐渐增大. 然而, 聚合时间过长会引起薄膜厚度的增加和氧化结构的过多, 使PANI CEs的导电率降低, 电子在PANI 薄膜中的传输阻抗增加, 进而影响其对I^?/I^3?的催化性能. 聚合时间为300 s 时制备出的PANI 薄膜作为染料敏化太阳能电池(DSSCs)对电极和以D149 为染料时, 获得的最高电池光电转换效率为5.30%, 可达到基于Pt 对电极电池效率的88%. 因此, 通过电化学方法制备的PANI CEs有望代替贵金属Pt CEs用于DSSCs中.     

聚苯胺纳米管在阳极氧化铝模板中电聚合的生长机理

利用阶跃电位、循环伏安等电化学方法，应用金属电沉积理论,研究聚苯胺纳米管在阳极氧化铝模板（AAO）内电聚合的生长机理.结果表明：电聚合初始，苯胺二维非扩散控制的瞬时成核生长形成聚苯胺晶胞链段单层,单层形成以后，聚苯胺的生长过程变为线性扩散控制. XRD实验进一步证实电聚合的聚苯胺同时包含结晶相和无定型相结构.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

KINETICS AND MECHANISM OF PHASE TRANSFER CATALYZED FREE RADICAL POLYMERIZATION OF METHYL ACRYLATE

The kinetics of free radical polymerization of methylacrylate (MA) was investigated using benzyltributylammonium chloride (BTBAC) as phase transfer catalyst and potassium peroxydisulfate as initiator at aconstant temperature, 60°C, in an inert atmosphere under unstirred condition. The effect of concentrations of the monomer, initiator and the catalyst on polymerization was discussed and a mechanism of polymerization has been proposed. The order with respect to the monomer, initiator, and phase transfer catalyst was found to be 2, 0.5, and 0.5, respectively.     

聚苯胺复合材料研究进展

综述了聚苯胺/无机物复合材料和聚苯胺/有机高聚物复合材料的合成方法，性能特征，并展望了聚苯胺复合材料的研究，应用前景。     

Polyaniline nanofibers fabricated by electrochemical polymerization: A mechanistic study

Polyaniline (PANI) nanofibers with interconnected network-like structures were electropolymerized on stainless steel substrates by galvanostatic electrolysis. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). The results show that PANI and gels (mixtures of oligomer, dopant and aniline) form simultaneously during the electrochemical deposition. The gels play an important role in the formation of PANI nanofibers. The PANI formed in the early stage of polymerization is subject to secondary growth along one dimension, since the nucleation sites are suppressed by the wrapped gels. The dendritic degree of PANI nanofibers is related to dopants, and the order is as follows: PANI-H₃PO₄ > PANI-H₂SO₄ > PANI-HNO₃. No nanofibers are obtained using CH₃COOH as dopants due to the high solubility of PANI-CH₃COOH.     

Polyaniline and polypyrrole: A comparative study of the preparation

Aniline and pyrrole have been oxidized with ammonium peroxydisulfate in aqueous solutions, in the presence of equimolar quantities of hydrochloric acid. The oxidation of pyrrole was faster; the induction period typical of aniline oxidation was absent in the case of pyrrole. As the proportion of oxidant-to-monomer molar concentration increased up to 1.5, the yield increased in both cases. Similarities between the two oxidations are illustrated and discussed. The oxidant-to-monomer molar ratio 1.25 is proposed to be the optimum stoichiometry, in the accordance with the data published in the literature. The conductivities of the polymers prepared were only slightly dependent on the oxidant-to-monomer ratio in the range 0.3-1.5, and were of the order of 10⁰ S cm⁻¹ for polyaniline and ∼10⁻²-10⁻¹ S cm⁻¹ for polypyrrole. Outside this interval, the conductivity of both polymers was reduced. Polyaniline having conductivity ∼10 S cm⁻¹ was produced in solutions of phosphoric acid of various concentrations. On the contrary, the conductivity of polypyrrole was reduced as the concentration of phosphoric acid became higher. The type of protonation is discussed with the help of FTIR spectra by analyzing the ammonium salts obtained after deprotonation. Sulfate or hydrogen sulfate anions produced from peroxydisulfate always constitute a part of the counter-ions.     

聚苯胺改性氮掺杂碳纳米管制备及其超级电容器性能

利用苯胺原位化学聚合合成聚苯胺包覆碳纳米管(CNTs), 再炭化处理制备氮掺杂碳纳米管(NCNTs).激光拉曼(Raman)光谱和X射线光电子谱(XPS)分析及透射电镜(TEM)观察表明, 苯胺包覆碳纳米管经炭化处理后, 得到以碳纳米管为核、氮掺杂碳层为壳, 具有核-壳结构的氮掺杂碳纳米管, 而碳纳米管本征结构未遭破坏. 研究表明, 随着苯胺用量的增大, 氮掺杂碳纳米管的氮掺杂碳层变厚, 氮含量从7.06%(质量分数)增加到8.64%, 而作为超级电容器电极材料, 随着氮掺杂碳层厚度降低, 氮掺杂碳纳米管在6 mol·L^-1氢氧化钾电解液中的比容量从107 F·g^-1增大到205 F·g^-1, 远高于原始碳纳米管10 F·g^-1的比容量, 且聚苯胺改性氮掺杂碳纳米管表现出较好的充放电循环性, 经1000次充放电循环后仍保持初始容量的92.8%~97.1%, 表明氮掺杂碳纳米管不仅通过表面氮杂原子引入大的法拉第电容和改善亲水性使电容量显著增大, 其具有的核壳结构特征也使循环稳定性增强。     

聚苯胺粒子悬浮液的电流变特性

将聚苯胺作为分散粒子，电绝缘油 分散介质组成电流变流体，研究了电场强度，温度等因素与ＥＲＦ的静态屈服应力和电流密度的关系。结果表明：τｓ和ｉ随电场强度的变化皆成指数关系。     

可溶性导电聚苯胺的研究进展

本文综述了可溶性导电聚苯胺的研究进展，评述了制备水溶性导电聚苯胺的各种方法，指出了水溶性聚苯胺的研究方向。     

自由基聚合中扩散效应分析

自由基聚合扩散效应包括“笼蔽效应”、凝胶效应和玻璃化效应,本文以聚合物大分子扩散理论发展为线索,首先讨论了基于粘度理论、标度理论、链缠结理论、自由体积理论等从宏观尺度描述自由基聚合扩散效应的模型,然后深入到微观分子尺度,从初级自由基的扩散行为讨论了“笼蔽效应”,基于增长自由基的三种扩散行为解释了凝胶效应和玻璃化效应,最后简单介绍了其他理论模型,并对理论未来的发展进行了展望。     

聚苯胺纳米复合材料的优良性能

聚苯胺纳米复合材料因结合了聚苯胺和纳米粒子的特殊性能,从而改善了基体的物理化学性能,赋予了材料前所未有的独特的性能,成为目前研究最为广泛的导电高分子纳米复合材料之一.本文基于国内外最新研究文献,结合典型事列详细综述了聚苯胺纳米复合材料在生物传感、催化、电磁、微波吸收和光电等方面呈现出的独特性能,简单评述了其在生物传感、催化、电磁、微波吸收、防腐等领域的应用前景.