导电聚苯胺电极柱识别天冬氨酸对映体的研究

以苯胺为单体,L-天冬氨酸(L-Asp)为模板分子,采用化学氧化法合成了掺杂L-Asp的导电聚苯胺(PAn).将PAn作为固定相填充到多孔陶瓷管中制备导电PAn电极柱,并以此电极柱作为工作电极.循环伏安图表明PAn电极柱具有良好的电化学活性.在电极柱上施加-0.6 V的还原电位,PAn中掺杂的L-Asp发生脱掺杂,从而在PAn膜上留下了与L-Asp完全匹配的空穴.由于PAn具有掺杂/脱掺杂完全可逆的独特性能,因此对带有分子印迹的PAn电极柱施加0.5 V的正电位后,由于存在强烈的分子印迹作用,L-Asp在电极柱上被富集,而D-天冬氨酸(D-Asp)的富集效果远低于L-Asp,从而实现对Asp对映体的识别.     

过氧化氢在磺酸二茂铁掺杂的聚苯胺上的电催化氧化

在含有磺酸二茂铁溶液中合成的聚苯胺（PAnFc）和不含磺酸二茂铁溶液中合成的聚苯胺（PAn）,在pH 5.0的缓冲溶液中均能催化过氧化氢的氧化,但PAnFc的催化活性高于PAn.催化效应的证据是过氧化氢在裸铂电极上的氧化电位为0.59 V(vs SCE),而在PAnFc电极仅是0.48 V,以及过氧化氢在PAnFc电极上的阳极峰电流是裸铂电极上的5.3倍.根据这种催化特性,用PAn和PAnFc固定葡萄糖氧化酶形成酶电极.实验结果表明,PAnFc酶电极的响应电流比PAn酶电极高得多,而且响应快.这是由于PAnFc在pH 5.0缓冲液中的电化学活性高于PAn,以及掺杂在聚苯胺中的磺酸二茂铁起着重要的电荷传递作用.     

乙醇对双核酞菁钴掺杂聚苯胺膜修饰电极特性的影响

研究了乙醇对双核酞菁钴(b i-CoPc)掺杂聚苯胺(PAn)膜修饰电极特性的影响。用循环伏安法(CV)考察了乙醇浓度不同时,玻碳电极(GC)上双核酞菁钴掺杂聚苯胺的电聚合过程,用紫外-可见吸收光谱(UV-V is)、红外光谱(FTIR)和扫描电子显微镜(SEM)表征了在氧化铟锡玻璃(ITO)电极上b i-CoPc掺杂的PAn膜,研究了乙醇对膜以及该膜修饰电极对溶液中分子氧电催化性能的影响。结果表明,乙醇对苯胺的电聚合有促进作用,有助于增加b i-CoPc掺杂量,膜的光谱特性发生变化,表面形貌更加均匀。乙醇存在下制备的修饰电极对溶液中分子氧的电催化活性明显提高。当乙醇含量为10%时,制备的电极催化能力最强。     

磁场及反应条件对十二烷基苯磺酸掺杂聚苯胺聚合成膜速率的影响

在恒定磁场(0.6 T)条件下, 采用过硫酸铵(APS)为引发剂, 在乳液体系中合成了十二烷基苯磺酸(DBSA)掺杂的聚苯胺(PAn). 借助石英晶体微天平(QCM)实时监测苯胺(An)在金电极表面聚合成膜过程, 探讨了磁场、APS浓度、DBSA浓度及反应温度对DBSA掺杂聚苯胺聚合成膜速率的影响. 实验结果表明, PAn在金电极表面的成膜速率随磁场强度的增加而增大; 由反应物浓度与PAn成膜速率的关系, 得出相应的动力学反应级数; 由PAn膜的增长速率与温度的关系, 得到成膜过程的活化能为41.08 kJ/mol. 考察了PAn聚合过程的UV-Vis光谱, 并与QCM所得的结果进行了比较. 结果显示, 在相同时间内, 磁场环境下合成的PAn的吸收强度大于无磁环境下合成的PAn.     

聚苯胺颗粒电极的制备与其电化学行为

采用循环伏安法,以含苯胺(An)的硫酸溶液为电解质,采用循环伏安技术在Pt微盘电极上得到随机、不连续沉积的聚苯胺(PAn)微颗粒和PAn膜.实验结果表明:H2SO4浓度、苯胺浓度、电位扫描上限和扫速对电化学合成随机、不连续沉积的PAn微颗粒具有重要影响.不连续随机沉积的PAn微颗粒电极与PAn膜电极在锂离子(Li-ion)电池电解质溶液中的行为有明显差异,不连续随机沉积的PAn微颗粒电极可以清楚地得到氧化还原电流峰,而PAn膜电极无法形成清晰的氧化还原电流峰.采用较缓慢扫描速度更有利于形成良好"结晶"的不连续PAn颗粒电极,该种电极可以同时具有高比能量和可逆性能.     

聚苯胺/膨胀石墨电极的制备及其用于聚合物半电池的研究

以膨胀石墨作为基底电极, 采用恒电位法合成了聚苯胺(PAn), 并探讨了在膨胀石墨基底电极上电聚合生成PAn的电化学条件. 结果表明: 聚合电位为0.8 V, 苯胺和硫酸的浓度分别为0.2和0.3 mol/L的条件下电聚合得到的PAn具有最佳的电化学活性. 分别以PAn/膨胀石墨和金属Mg为工作电极, 铂片为辅助电极, 饱和甘汞电极为参比电极组成三电极体系, 测定PAn/膨胀石墨和Mg在0.1 mol/L的NaNO₂, MgCl₂, Mg(NO₃)₂及磷酸盐缓冲液(PBS)等不同电解质溶液中的极化曲线, 实验结果表明电解液的种类对PAn的稳定性影响不大, 而Mg在0.1 mol/L NaNO₂溶液中的稳定性最高. 以PAn/膨胀石墨作为阴极, 金属Mg为阳极, 0.1 mol/L NaNO₂为电解液组装成Mg│NaNO₂│PAn电池, 并考察了基于该聚合物电极的电池在电流密度为30 mA•g^－1时的恒电流放电行为. 相比于其它电解液, 该电池在0.1 mol/L NaNO₂电解液中具有较高的开路电位(1.84 V)和放电比容量(0.19 Ah•g^－1).     

间甲酚溶液中掺杂聚苯胺的氧化-还原行为研究

在有、无外加恒定磁场(0.4T)条件下,采用乳液聚合法合成了十二烷基苯磺酸掺杂聚苯胺(PAn),通过傅立叶红外光谱(FT-IR)、在有/无外电场作用下产物/m-cresol溶液的电导率、pH及其颜色随温度变化的分析表征,系统研究了温度对PAn/m-cresol溶液中PAn氧化-还原(掺杂-脱掺杂)行为的影响.溶液电导率和pH的测试结果显示,溶液电导率与溶液中游离掺杂酸的浓度成正比,PAn的掺杂度随温度的升高而降低,随温度的降低而增大,且在相同温度下,有、无外电场作用时PAn/m-cresol溶液的电导率存在突跃.与无磁场条件下合成的PAn所制备的m-cresol溶液相比,磁场条件下合成的PAn所制备的m-cresol溶液电导率的突跃更加显著.经脱掺杂处理后的PAn/m-cresol溶液的电导率均较低,对温度变化的响应极其微弱,且在有、无外电场作用时不发生突跃.分析认为,这是由于外电场作用下m-cresol溶液中掺杂态的PAn分子发生了取向重排,而脱掺杂的PAn则无此变化.PAn在外电场作用下的取向重排及氧化-还原性均与其掺杂程度相关,掺杂程度越高,氧化-还原及取向重排越显著.     

Pt/PAn/Ti电极的制备及对甲醛的电催化氧化

通过循环伏安的电化学方法在金属钛基体上先后进行苯胺的聚合和金属铂的电化学沉积,得到以金属钛为基体的聚苯胺载铂电极(Pt/PAn/Ti),并通过扫描电镜和循环伏安法对该电极进行了表征。通过研究甲醛在该电极上的电催化氧化行为,考察了载铂量对甲醛氧化效果的影响及PAn在电催化氧化甲醛的过程中所起的作用。结果表明,载铂量与甲醛的氧化有一定的关系,PAn的存在使得铂微粒分散程度更好,有效面积更大,与相同铂沉积量的Pt/Ti电极相比,甲醛在其上的正向扫描氧化峰电流密度增加了2.3倍,电位负移了40mV;反向扫描氧化峰电流密度增加了5倍,电位负移了30mV。同时,PAn的存在也增强了电极的抗中毒能力。     

掺杂率对乳液聚合制备聚苯胺结构性能的影响

对乳液聚合的十二烷基苯磺酸(DBSA)掺杂聚苯胺(PAn)进行不同pH值溶液浸泡处理。采用元素分析、红外光谱分析、X射线衍射及热失重分析等手段，研究了不同掺杂率对PAn结构性能以及PAn在普通有机溶剂中的溶解性能和导电性能的影响。结果表明：随DBSA掺杂率的增加，PAn的电导率及其在三氯甲烷中的溶解度增加，带有烷基长链的DBSA使PAn形成以DBSA为间隔的有序层状结构；而且合成的PAn-DBSA热稳定性良好。     

PmClAn基膜修饰电极的电化学及催化性质研究

聚苯胺作为电极修饰材料 ,已在传感器上显示出广泛的应用前景[1～ 4 ] .异丙醇 ( i- P)氧化[5,6 ] 是个较简单的反应 ,被广泛作为电催化研究的模型反应 .目前 ,i- P电化学氧化的研究集中于 Pt的多晶或单晶电极[7～ 9] ,Gonzales等 [10 ] 报道了 Pt- Sn共沉积的 PAn膜修饰电极上的异丙醇电氧化 ,但对复合材料的微观结构仍欠研究 .本文讨论 Pm Cl An基质性质对 Pt电沉积的影响 ,并探讨了 i- P在沉积 Pt微粒的 Pm Cl An功能膜电极上的氧化情况 .1　实验部分1 .1　电极的制备　聚间氯苯胺 ( Pm Cl An,本征态 ud,HCl掺杂态 d)采用乳液聚…     

聚苯胺对2,5-二巯基-1,3,4-噻二唑氧化还原反应的电化学催化作用的循环伏安研究

研究了聚苯胺(PAn)膜电极在2,5-二巯基-1,3,4-噻二唑(DMcT)溶液中电化学处理或浸泡后的循环伏安(CV)曲线的变化规律.实验结果表明,PAn膜电极在DMcT溶液中进行电化学处理或浸泡过程可使DMcT进入PAn膜内部与PAn形成复合物.PAn对DMcT的电化学催化作用可能和二者之间形成的电子给体-受体复合物有关.该复合物的电化学氧化还原特性不同于PAn和DMcT,其氧化还原反应速率和可逆性均优于DMcT.     

聚苯胺对2,5—二巯基—1,3,4—噻二唑氧化还原反应的电化学？…

研究了聚苯胺（ＰＡn）膜电极在２,５－二巯基－１,３,４－噻二唑（ＤＭcＴ）溶液中电化学处理或浸泡后的循环伏安（ＣＶ）曲线的变化规律。实验结果表明,ＰＡn膜电极在 ＤＭcＴ溶液中进行电化学处理或浸泡过程可使ＤＭcＴ进入ＰＡn膜内部与ＰＡn形成复合物。ＰＡn对ＤＭcＴ的电化学催化作用可能和二者之间形成的电子给体－受体复合物有关。该复合物的电何尝氧化还原特性不同于ＰＡn对ＤＭcＴ的电化学催化作用可能和得之间形成的     

聚苯胺薄膜修饰电极对抗坏血酸的电催化氧化

本文表明聚苯胺(PAn)薄膜修饰电极对水溶液中的抗坏血酸(AH_2)在较宽的pH范围和较宽的浓度范围内均有良好的电催化氧化作用, 为EC平行催化过程。利用旋转圆盘电极(RDE)进行了催化过程动力学分析, 求出了催化反应动力学参数。在抗坏血酸浓度10~(-2)～10~(-6) mol·L~(-1)范围内, 催化峰电流与AH_2浓度均成良好的线性关系, 且PAn薄膜修饰电极具有很好的稳定性, 有应用分析抗坏血酸的意义。     

碳纸负载电极在乳液法合成聚苯胺电化学性能分析中的应用

首次采用碳纸负载聚苯胺(PAn)为工作电极,探讨了反应时间对乳液法合成PAn电化学性能(循环伏安、交流阻抗及塔菲尔曲线)的影响,并通过对产物电导率、产率及特性粘度的对比分析,印证了产物电化学性能的表征结果.实验结果表明,循环伏安曲线均能有效表征出PAn的三对氧化还原特征峰,交流阻抗曲线均出现一个几乎完整的半圆;且产物的循环伏安、交流阻抗、塔菲尔、产率及电导率随反应时间的变化趋势一致,在反应5h时,PAn的各项性能指标较好.结果显示,利用碳纸作为负载电极,可以对乳液法合成PAn的电化学性能实施有效的实时表征.     

Template‐free synthesis of polyaniline nanobelts as a catalytic counter electrode in dye‐sensitized solar cells

Polyaniline (PAn) nanobelts were synthesized by simply mixing aniline and hydrochloric acid aqueous solution with ammonium peroxydisulfate and hydrochloric acid aqueous solution at room temperature without any templates. The PAn nanobelt paste with polytetrafluoroethylene as binder is proper for low‐cost and efficient casting processes such as doctor blade method, screen printing, spin‐casting, and even roll‐to‐roll painting. The porous network structure of the PAn nanobelt counter electrode was obtained after drying the paste on the conductive glass. The as‐prepared PAn nanobelt counter electrode showed nearly equivalent electrochemical catalytic activity as that of thermal decomposed Pt counter electrode, owing to the well‐connected conductive network and high active surface area. The power conversion efficiency of dye‐sensitized solar cell with PAn nanobelt counter electrode attained 90% of the value of the cell with Pt counter electrode. Copyright © 2014 John Wiley & Sons, Ltd.     

纳米尺度TiO2聚苯胺多孔膜电极光电化学研究

用光电流作用谱，光电流－电势图等光电化学方法研究了ＴｉＯ２／聚本胺复合多孔膜电极在不含氧化还原和含有没氧化还原对体系中的光电转换过程。结果说明，ＴｉＯ２／聚苯胺复合多孔膜电极为双层ｍ－型半导体结构，ＴｉＯ２多孔膜的禁带宽度为３．２ｅＶ，外层聚苯胺膜的禁带宽度为２．８８ｅＶ。     

Integration of polyaniline/poly(acrylic acid) films and redox enzymes on electrode supports: an in situ electrochemical/surface plasmon resonance study of the bioelectrocatalyzed oxidation of glucose or lactate in the integrated bioelectrocatalytic systems

Electropolymerization of aniline in the presence of poly(acrylic acid) on Au electrodes yields a polyaniline/poly(acrylic acid) composite film, exhibiting reversible redox functions in aqueous solutions at pH = 7.0. In situ electrochemical-SPR measurements are used to identify the dynamics of swelling and shrinking of the polymer film upon the oxidation of the polyaniline (PAn) to its oxidized state (PAn(2+)) and the reduction of the oxidized polymer (PAn(2+)) back to its reduced state (PAn), respectively. Covalent attachment of N(6)-(2-aminoethyl)-flavin adenin dinucleotide (amino-FAD, 1) to the carboxylic groups of the composite polyaniline/poly(acrylic acid) film followed by the reconstitution of apoglucose oxidase on the functional polymer yields an electrically contacted glucose oxidase of unprecedented electrical communication efficiency with the electrode: electron-transfer turnover rate approximately 1000 s(-1) at 30 degrees C. In situ electrochemical-SPR analyses are used to characterize the bioelectrocatalytic functions of the biomaterial-polymer interface. The current responses of the bioelectrocatalytic system increase as the glucose concentrations are elevated. Similarly, the SPR spectra of the system are controlled by the concentration of glucose. The glucose concentration controls the steady-state concentration ratio of PAn/PAn(2+) in the film composition. Therefore, the SPR spectrum of the film measured upon its electrochemical oxidation is shifted from the spectrum typical for the oxidized PAn(2+) at low glucose concentration to the spectrum characteristic of the reduced PAn at high glucose concentration. Similarly, the polyaniline/poly(acrylic acid) film acts as an electrocatalyst for the oxidation of NADH. Accordingly, an integrated bioelectrocatalytic assembly was constructed on the electrode by the covalent attachment of N(6)-(2-aminoethyl)-beta-nicotinamide adenine dinucleotide (amino-NAD(+), 2) to the polymer film, and the two-dimensional cross-linking of an affinity complex formed between lactate dehydrogenase and the NAD(+)-cofactor units associated with the polymer using glutaric dialdehyde as a cross-linker. In situ electrochemical-SPR measurements are used to characterize the bioelectrocatalytic functions of the system. The amperometric responses of the system increase as the concentrations of lactate are elevated, and an electron-transfer turnover rate of 350 s(-1) between the biocatalyst and the electrode is estimated. As the PAn(2+) oxidizes the NADH units generated by the biocatalyzed oxidation of lactate, the PAn/PAn(2+) steady-state ratio in the film is controlled by the concentration of lactate. Accordingly, the SPR spectrum measured upon electrochemical oxidation of the film is similar to the spectrum of PAn(2+) at low lactate concentration, whereas the SPR spectrum resembles that of PAn at high concentrations of lactate.     

DNA-templated assembly and electropolymerization of aniline on gold surface

Biomolecule template gives new opportunities for the fabrication of novel materials with special features. Here we report a route to the formation of DNA–polyaniline (PAn) complex, using immobilized DNA as a template. A gold electrode was first modified with monolayer of 2-aminoethanethiol by self-assembly. Thereafter, by simply immersing the gold electrode into DNA solution, DNA molecules can be attached onto the gold surface, followed by the DNA-templated assembly and electropolymerization of protonated aniline. The electrostatic interactions between DNA and aniline can keep the aniline monomers aligning along the DNA strands. Investigations by surface plasmon resonance (SPR), electrochemistry and reflection–absorption UV/Vis–Near IR spectroscopy substantially convince that PAn can be electrochemically grown around DNA template on gold surface. This work may be provides fundamental aspects for building PAn nanowires with DNA as template on solid surface if DNA molecules can be individually separated and stretched.