Au/PATP/PANI膜电极和Au/PATP/PANI/TiO2膜电极的光电化学

聚苯胺（PANI）是一种结构、 性质不同于聚乙炔和聚吡咯的新型导电高聚物,有着十分广泛的应用[1,2].近年来利用光电化学研究聚苯胺的电子结构、 掺杂情况引起人们的重视[3～5].在酸性溶液中电聚合制备聚苯胺的循环伏安曲线上出现两对氧化还原峰,其峰值电位分别为E11/2=0.13 V和E21/2=0.7 V(对饱和甘汞电极).通过改变电极电位,可获得部分氧化态、还原态、氧化态等3种状态的聚苯胺.部分氧化态具有金属导电性,还原态和氧化态均为绝缘体.本文测量3种状态聚苯胺膜电极的光电响应,首次得到其光电流谱,发现聚苯胺一些新的光电化学实验结果.提出了覆盖绝缘体的金属内发射的光电化学模型.同时,在聚苯胺膜上电沉积纳米TiO2微粒膜,得到广谱区的复合光电材料.     

缓冲液中聚苯胺的电化学活性和电致变色

使用循环伏安法、恒电流充放电和现场光谱电化学法研究了聚苯胺在氯化钠溶液、磷酸氢钠缓冲液和由氯化锌和氯化铵组成的溶液中的电化学活性和电致变色。在pH457的1mol×dm-3NaCl溶液中,聚苯胺膜的颜色几乎不随电位而变化,循环伏安图上无氧化还原峰,所以聚苯胺仅有很低的电化学活性。在pH457、640、738的磷酸氢钠缓冲溶液中,循环伏安图上有氧化还原峰。随pH值升高,它们的峰电位向负电位方向移动。根据循环伏安图的面积,聚苯胺在02mol×dm-3磷酸氢钠缓冲溶液中的电化学活性,即氧化还原电量约是相同pH值的1mol×dm-3NaCl溶液中的3倍。在pH738、640和pH457的02mol×dm-3磷酸氢钠缓冲液中,聚苯胺吸收峰的波长移动的起始电位分别为010V、030V和040V(vs.AgAgCl电极,饱和KCl溶液)。这种电位移动的趋势与循环伏安图上的氧化还原峰的电位移动相一致。在pH640和pH457的02mol×dm-3磷酸氢钠缓冲溶液中,聚苯胺的可见光谱图上出现一个与电位有关的等吸收点。聚苯胺膜在pH475和pH640的02mol×dm-3磷酸氢钠缓冲液中,当电位从060V下降到-020V(vs.AgAgCl电极,饱和KCl溶液)时,聚苯胺膜的颜色从紫红色变到兰色、绿色和黄色。在pH440、457和492的由25mol×dm-3ZnCl2和30mol×dm-3NH4Cl组成的溶液中,聚苯胺的循环伏安图上均有     

聚苯胺纳米点的氧化还原态与其库仑台阶效应

应用电化学恒电位法结合模板法制备聚苯胺纳米点阵列,导电原子力显微镜研究处于不同氧化还原态的聚苯胺纳米点的I～V特性,发现只有处于部分氧化态(导电态)的聚苯胺纳米点才出现库仑台阶效应,还原和全氧化态聚苯胺纳米点不显示库仑台阶.初步探讨了上述现象.     

聚苯胺膜修饰电极对儿茶酚及对苯二酚的催化氧化

研究了电化学条件下聚合生成的聚苯胺膜对儿茶酚及对苯二酚的催化氧化。实验分析了影响电催化的几个因素：聚合电位、膜厚、溶液酸度及底物浓度，同时分析和比较了聚苯胺膜对两种不同多酚类化合物的催化反应。提出电化学测试分析多酚类化合物的可能性。     

TiO_2聚苯胺复合膜的光电化学

利用电化学方法制备了TiO2 聚苯胺 (PANI)复合膜 .该膜具有比TiO2 或PANI膜更宽的吸收谱区 ,并且不同于利用聚苯胺光敏化的TiO2 膜 ,表现为两者复合材料膜的性质 .扫描电镜图表明 ,TiO2 微粒不完全覆盖着PANI膜 .根据TiO2 微粒光电流谱带的阈值能可得复盖在部分氧化态聚苯胺膜上的TiO2 微粒的禁带宽度为 3.0eV .部分氧化态聚苯胺膜的光电流谱遵循Fowler定律 ( 1/2 ～hυ成线性 ) .通过Fowler图得出部分氧化态聚苯胺的绝缘母体禁带宽度为 3.33eV ,并证实该绝缘母体为还原态聚苯胺 .从Mott Schottky图得到在 0 .0 5mol/LK3Fe(CN) 6 /K4 Fe(CN) 6 溶液中 (pH =8.52 )部分氧化态聚苯胺的平带电位为 0 .13V ,掺杂浓度为 5.3× 10 18cm- 3;TiO2 PANI复合膜的平带电位为 - 0 .6 5V ,掺杂浓度为 9.1× 10 19cm- 3.解释了TiO2 PANI复合膜的光电化学过程并描绘出其能带图 .利用TiO2 PANI复合膜能够有效地光降解苯酚溶液 .     

聚{吡咯-2,5-二[(对二甲氨基)苯甲烯]}的电化学和原位拉曼光谱

采用电化学循环伏安法（CV）和原位拉曼光谱（in situ Raman）对窄能隙共轭高分子聚{吡咯 2,5 二[(对二甲氨基)苯甲烯]}（PPDMABE）的电化学行为进行了研究.结果表明,在不同pH值NaNO3溶液中, PPDMABE的电化学氧化还原过程中存在吡咯环的氧化态结构与芳式和醌式结构之间的转变.聚合物在氧化态时吡咯环主要以氧化态存在,而还原态以芳式和醌式结构吡咯环为主.PPDMABE在酸性和中性介质中氧化态吡咯环以质子化的状态存在,而在碱性溶液中氧化态吡咯环既有质子化态,又有去质子化态的.在酸性条件下,PPDMABE较易发生氧化还原反应,而在碱性条件还原反应则较难发生.     

制备条件对PANI/PATP/Au和TiO_2-PANI/PATP/Au膜光电化学性能的影响

应用电化学方法在不同条件下制备聚苯胺 (PANI)膜和TiO2 -PANI复合膜 ,并对其光电化学性能进行研究 .实验表明 ,制备条件是影响膜光电化学性能的重要因素 .对氨基硫酚 (PATP)的组装有利于改善PANI膜的附着力 ;部分氧化态PANI膜的光电化学响应明显优于还原态和氧化态PANI膜的光电化学响应 ;部分氧化态PANI膜的厚度对其光电化学性能有一最佳值 ;热处理虽然有利于改善TiO2 的光电化学性能 ,但温度太高 ,将破坏PANI膜的表面结构 ,对于TiO2 -PANI复合膜有一最佳的热处理温度 .优化制备条件大可改善TiO2 -PANI复合膜和PANI膜的光电化学性能     

现场拉曼光谱研究聚吡咯的去质子化和氧化降解

利用电化学现场拉曼光谱结合循环伏安法,研究了中性和碱性溶液中聚吡咯（ＰＰＹ）膜的行为及其结构．结果表明,氧化态ＰＰＹ中吡咯环Ｎ原子上的Ｈ失去发生去质子化,形成一种醌式结构．由于该醌式结构的出现使ＰＰＹ的Ｃ＝Ｃ伸缩振动峰发生分裂,且因该醌式结构不能被进一步氧化,以致ｐＨ值增大,去质子化程度提高,ＰＰＹ变得较难被氧化,而使其可逆性也受到一定程度的破坏,在ｐＨ＝１３的强碱性溶液中,ＰＰＹ膜在正于ＯＶ的电位区间内发生降解,该降解过程可能涉及到ＰＰＹ的吡咯环单元结构的破坏．     

聚苯胺在高pH值溶液中的电化学活性

由于聚苯胺(PANI)独特的质子酸掺杂机制, 其在高pH值溶液中会发生去质子化过程, 导致失去导电性和电化学活性, 故普通PANI只有在酸性介质中(pH<4)才具有电化学氧化-还原活性, 这成为PANI应用的一大障碍. 为解决PANI在高pH值溶液中的“失活”问题, 人们提出了各种各样的方法. 从基于质子酸掺杂机理和基于电荷转移机理的两大解决途径入手, 就提高PANI在高pH环境中电化学活性的方法进行了系统综述, 重点评述了自掺杂、高分子酸掺杂和碳纳米管掺杂PANI的制备方法、电化学特性以及提高电化学活性的作用机制, 并指出了提高PANI高pH环境下的电化学活性所存在的难点及今后的研究方向.     

恒电位条件下制备聚苯胺PAn及其电化学行为

恒电位条件下在玻碳电极上用电化学聚合法制备了聚苯胺膜，研究了聚合条件如聚合电位，聚合介质，苯胺浓度等对聚苯胺膜化学性质的影响，从而确定了制备聚苯胺的最佳聚合方法和条件，并讨论了在不同支持电解质溶液中和不同ＰＨ值条件下ＰＡｎ膜的循环伏安行为，认为５５０ｍＶ出现的氧化还原峰与阴离子的掺杂有关。     

碱性条件下聚苯胺形貌的调控

近几年,共轭聚合物的微/纳米结构(如:纤维、管、球等)由于在低维系统和决定材料性质及应用方面的重要作用而备受瞩目[1~3].其潜在的应用领域包括分子导线、化学传感、气体分离及光电子器件等.聚苯胺(PANI)[4]具有优异的电学性能,良好的加工性和突出的环境稳定性,是典型的共轭聚     

Scanning force microscopy and effective medium theory study of free-standing polyaniline thin films

The technique of scanning force microscopy was used to study the nanometer-scale structure of NMP cast films of polyaniline. Noncontact mode images provide direct evidence that polyaniline prepared in this form is a granular conductor. The films were found to consist of micrograins whose size and density were determined by the pH of the acid solution used to protonate the films. At pH 7, the polyaniline films exhibited a mostly disordered structure, with small 2–10 nm particles visible. Protonation at pH 5 to pH 3 resulted in partial agglomeration of the primary particles into larger bundles, with sizes up to 75 nm. Treatment in solution pHs of 2 or less resulted in films consisting of close-packed bundles of dimension 20–30 nm. The conductivity of the films exhibited a sharp rise beginning with protonation at pH 2 or less. Effective medium theory (EMT), was used to model the macroscopic conductivity of these films based on the SPM measured microscopic film structure. Using the size and size distribution of polymer micrograins or bundles in a modified EMT, we are able to obtain predicted conductivities that are close to the measured values for these films. © 1995 John Wiley & Sons, Inc.     

Polyaniline pH Electrodes

Polyaniline-coated Pt, Pd, and graphite electrodes have been studied. Their potential relationship to pH follows the same principle as the pH glass electrode. They are solid state involving no redox reactions. The potential is derived from the surface charge density caused by protonation or deprotonation. They act as capacitors. The nonprotonated form of polyaniline was used for pH 6.8 to 1.2 and the protonated form of polyaniline was used for pH 6.8 to 13.0. Three regions of curves (acid, neutral, and alkaline) were obtained. The polyaniline-coated graphite electrode is recommended. It offers the advantage of sturdiness and may be used in microscale in HF solution, at high pressure. At pH 2.2, approximately 4,200 H⁺ions were adsorbed by polyaniline per nm². An insignificant number of H⁺ions were adsorbed by polyaniline at pH 6.2; this is close to its isoelectric point.     

Solid-state pH nanoelectrode based on polyaniline thin film electrodeposited onto ion-beam etched carbon fiber

An ultramicro pH sensor has been constructed based on a thin polyaniline film that was electrochemically deposited onto a carbon fiber nanometer-size electrode. The substrate nanoelectrodes were fabricated using ion-beam conically etched carbon fibers with tip diameters ranging ca. from 100 to 500 nm. The polyaniline film was deposited from HCl solution containing the aniline monomer by cycling the potential between −0.2 and +1.0 V. The electromotive force (emf) signal between the pH sensitive polyaniline-coated nanoelectrode and an Ag/AgCl reference electrode was linear over the pH range of 2.0-12.5 with a slightly super-Nernstian slope of ca. −60 mV/pH unit. Response times ranged from several sec at pHs around 7 up to 2 min at pH 12.5. The proposed pH nanoelectrode displayed high ion selectivity with respect to K⁺, Na⁺, Ca²⁺, and Li⁺, with log K_H,M values around −12 and has a working lifetime of about 20 days. Key parameters important for the pH nanoelectrode performance, including polyaniline film preparation, selectivity, response time, temperature dependence, relative coating thickness, stability, and reproducibility, have been characterized and optimized. The performance of the pH nanoelectrode was examined by measuring the pH of several real samples including body fluids (serum, urine) and low ionic strength water samples (rain, deionized and tap water). The results agreed very well with those obtained by using commercial glass pH electrodes. The proposed pH nanoelectrode demonstrated attractive properties and seems particularly promising for use under physiological conditions.     

聚苯胺/钴-氧化钴膜作传感元件的pH传感器的性能

本文研究了在玻碳电极上修饰不同物质所制得的pH传感器,通过电位滴定的方法比较得出先修饰聚苯胺,再修饰钴-氧化钴膜的电极对pH有较好的响应,能代替玻璃电极应用在实际样品测定中。探究了最佳修饰条件为：先在0.1mol/L苯胺的盐酸（1mol/L）溶液中, 电位范围为-0.2~1.0V,以100 mV/s 的扫描速度循环伏安扫描 10圈修饰聚苯胺膜;接着在含2.0×10-4 mol/LCo2+的PBS （pH=7.5）缓冲溶液中, 电位范围为-1.2~1.2V,以100 mV/s 的扫描速度循环伏安扫描 5圈修饰钴-氧化钴膜。得到的修饰电极响应斜率为-61.60 mV/pH,响应范围pH 0.5~13。     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

Polyaniline film formation in hexadecyl trimethyl ammonium bromide admicelles on hydrous zirconia surface

Formation of a thin polyaniline film on hydrous zirconia (ZrO2) surface was carried out using adsorbed surfactant bilayers on ZrO2 as reaction sites. Aniline was adsolubilized in hexadecyltrimethylammonium bromide (HDTAB) admicelles formed on the surface of ZrO2 by adsorption. Subsequent polymerization of the adsolubilized aniline monomer showed effective conversion of aniline to polyaniline. The formation of the polyaniline coated ZrO2 has been confirmed by UV-visible spectroscopy, FT-IR spectroscopy, and conductivity measurements. Various parameters involved during the adsorption process were studied. Selection of pH 9.0 as the pH of all experimental feed solutions was governed by the knowledge of point of zero charge (PZC) of ZrO2. Effect of aniline concentration on HDTAB adsorption was studied and it was observed that increase in aniline concentration decreased the amount of HDTAB adsorbed on ZrO2. Addition of salt (0.05 M NaCl) in the feed solution increased HDTAB adsorption and drastically reduced the effect of aniline concentration on HDTAB adsorption.     

Electrochemical properties of a two-component DNA-polyaniline film at the surface of glassy carbon electrode

Aniline electropolymerization on a DNA-modified glassy carbon electrode gives rise to a stable composite DNA-polyaniline film possessing redox activity over a wide range of pH values. The heights and potentials of the redox peaks linearly depend on pH in the pH 3.0–8.0 range. It was established that the inclusion of DNA into the polyaniline composition enhances considerably the film conductivity and capacitance in the weakly acid and weakly alkaline pH regions; this effect is most pronounced for the reduced polymer form. The properties of the prepared DNA-polyaniline film point to its promise for the use in electrochemical biosensors.     

Assembly of tobacco mosaic virus into fibrous and macroscopic bundled arrays mediated by surface aniline polymerization

One-dimensional (1D) polyaniline/tobacco mosaic virus (TMV) composite nanofibers and macroscopic bundles of such fibers were generated via a self-assembly process of TMV assisted by in-situ polymerization of polyaniline on the surface of TMV. At near-neutral reaction pH, branched polyaniline formed on the surface of TMV preventing lateral association. Therefore, long 1D nanofibers were observed with high aspect ratios and excellent processibility. At a lower pH, transmission electron microscopy (TEM) analysis revealed that initially long nanofibers were formed which resulted in bundled structures upon long-time reaction, presumably mediated by the hydrophobic interaction because of the polyaniline on the surface of TMV. In-situ time-resolved small-angle X-ray scattering study of TMV at different reaction conditions supported this mechanism. This novel strategy to assemble TMV into 1D and 3D supramolecular composites could be utilized in the fabrication of advanced materials for potential applications including electronics, optics, sensing, and biomedical engineering.     

In situ study of the conductivity of the electrochemically deposited polyaniline film using a dual-disk microelectrode

A conductivity equation based on the dual-disk microelectrode was derived. This electrode was used for in situ measurement of the conductivity of polyaniline. Some factors such as electrochemical potential, solution pH, scan rate and over-oxidation, which influence the conductivity of polyaniline, were conveniently controlled by this electrode. Experimental results proved that this electrode is very useful for measuring the relative conductivity in situ and studying the conducting mechanism of conductive polymers.