二磺酸掺杂高热稳定性导电聚苯胺的合成及性能

以有机二磺酸作为掺杂剂合成了具有高热稳定性的二磺酸掺杂导电聚苯胺。研究了反应时间、温度、酸/苯胺摩尔比等因素对产率、产物的导电率与分子量的影响。利用微波加热的方法测试有机二磺酸掺杂聚苯胺的热稳定性能，结果表明：有机二磺酸掺杂的导电聚苯胺在微波场中升温速率快，并且具有良好的反复升温性能。     

聚苯胺与聚苯甲酰胺的共混研究

在制得可溶性聚苯胺基础上，研究了聚苯胺与聚苯甲酰胺在二甲基乙酰胺（含３．５％ＬｉＣｌ）中的共混溶液行为并绘出其三元相图。研制了不同配比的聚苯胺／聚苯甲酰胺共混膜。测试结果表明，在聚苯胺中混入２０％ＰＢＡ后其拉伸强度可增加２～３倍且其导电率可达７．５Ｓ／ｃｍ。考察了混合比对共混薄膜的导电率和力学性能的影响．ＳＥＭ及Ｘ－衍射结果表明聚苯胺／聚对苯甲酰胺共混物存在着明显的微观相分离．     

聚2，5-二甲氧基苯胺的合成与表征

报导了聚2，5-二甲氧基苯胺（P25DMAn）的化学与电化学合成，并用元素分析、FTIR、UV－VIS吸收光谱、电导率测定以及电化学等手段对该聚合物进行了表征．P25DMAn类似聚苯胺（PAn）的结构，是由其单体通过氮原子N在对位上键合而成.P25DMAn是一种能溶于多种有机溶剂如THF、CH2Cl2、CHCl3、DMSO、DMF等．并具有极好的环境稳定性，优良的电活性和相当高的电导率的高聚物．因此，P25DMAn是一种很有应用前景的新的导电高聚物．     

以对甲基苯磺酸做掺杂剂电化学法合成聚苯胺的性能

热稳定性;溶解性;以对甲基苯磺酸做掺杂剂电化学法合成聚苯胺的性能     

聚1,5-二氨基蒽醌二次锂电池正极材料研究

采用化学氧化方法合成了聚1,5-二氨基蒽醌(PDAAQ)并用于二次锂电池.借助红外光谱确定其分子结构,实验测得材料的平均粒径为7.9μm,比表面积为8.9 m2.g-1,具有0.8 S.cm-1的电导率,符合作为电极材料使用的基本要求;电化学测试表明,作为二次锂电池正极材料使用时,聚合物重复单元中除了醌基团与Li+所发生的电化学氧化还原反应外,聚苯胺导电骨架也对PDAAQ的能量密度和循环性产生贡献.充放电曲线则进一步确定了聚苯胺骨架与醌基团协同作用的存在,实验表明,在Li(CF3SO2)2N/PC+DGDM电解液中,基于活性材料PDAAQ的首次放电容量达到221 mAh.g-1,经过40次充放电循环,容量保持率为80%,因此聚1,5-二氨基蒽醌具有较大应用潜力.     

聚苯胺/PA-6导电复合膜的电化学合成与性能

用电化学复合法，以聚己内酰胺为膜基，通过氟硼酸掺杂，使苯胺电解聚合，制成一种新型的聚苯胺／聚己内酰胺（ＰＡｎ／ＰＡ－６）复合膜，考察了电流密度、掺杂剂浓度及苯胺浓度等因素对导电复合膜的电导率、机械性能的影响。     

二次掺杂对聚苯胺导电复合物性能的影响

研究了聚苯胺与（苯乙烯－丁二烯）三嵌段共聚物或氯碘化聚乙烯复合物在间甲酚二次掺杂前后电导率的变化（提高２个数量级），根据二次掺杂使聚苯胺复合物增强永久形变和断面形貌脆断一次掺杂使卷曲的聚苯胺链展开并通过这间的弱相互作用而自行组成导电能通路，复合物二次掺杂前后的抗张强度和伸长率变化不大，说明其主链间的弱相互作用对应力无贡献，此外，还研究了二次掺杂对复合物在中性和酸必南中电致变色活性的影响。     

导电含硫材料/聚苯胺复合物作为镁二次电池的正极材料

使用通过简单加热聚丙烯腈(PAN)和硫单质而得到的导电含硫材料(conductive sulfur-containing material, CSM)及其与聚苯胺(PAn)的复合物作为镁二次电池的正极材料. X射线衍射(XRD)和傅立叶红外光谱(FT-IR)测试表明, 导电含硫材料的结构由类似石墨的微晶相及无定形相所组成, 材料骨架为含有S—S键的脱水嘧啶型基质. 该导电含硫材料与聚苯胺复合并掺杂Cu(II)后, 其放电比容量和电化学可逆性大大提高, 放电比容量可达117.3 mAh·g-1, 22次循环后容量保持大约78％(相对于第二次放电容量). 聚苯胺不仅起到电化学催化剂的作用, 同时也是电极活性物质, 并且在分子水平上改善了活性材料的导电性能. 该复合物研究结果为镁二次电池正极材料结构设计的开发提供了新的思路.     

1,5-二硝基蒽醌电化学还原制备──1,5-二氨基-4,8-二羟基蒽醌的研究(英文)

采用循环伏安法、稳态极化曲线法和恒电位电解法相结合的实验手段,研究了１,５－二硝基蒽醌（１,５－ＤＮＡ）在硫酸溶液中、汞齐化铜电极上阴极还原制备１,５－二氨基－４,８－二羟基蒽醌（１,５－ＤＡ－４,８－ＤＨＡ）的电化学反应性能．结果表明：在１２．７５ｍｏｌ／ＬＨ２ＳＯ４和１４０℃温度下,１,５－ＤＮＡ在汞齐化铜阴极表面上具有反应物强吸附和不可逆随后化学反应的特征．电解最后的产物经红外光谱测定为１,５－二氨基－４,８－二羟基蒽醌,平均电流效率为７８％,产率为７２％．１,５－ＤＮＡ直接电化学还原的行为与电极材料、酸浓度、添加剂、反应物浓度等有关．     

分散剂类型对聚苯胺粒径分布和电化学特性的影响

采用化学氧化聚合法以苯胺为单体、过硫酸铵为氧化剂,在不同分散剂体系中合成聚苯胺,考察分散剂对聚苯胺性能的影响。通过激光粒度仪、傅里叶红外吸收光谱、四探针电阻仪和电化学工作站等测试手段研究聚苯胺的结构、导电性、粒径分布及电化学性能。结果表明：分散剂能降低聚苯胺的粒径分布,提高聚苯胺的导电性和电化学稳定性;当分散剂聚乙二醇占苯胺单体质量的20％时,聚苯胺的平均粒径为3．85μm,导电率为4．68S／cm,极化电位为0．73V。     

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.     

苯胺共聚物/环氧共混体系防腐蚀行为的研究

以苯胺与邻甲氧基苯胺为单体,采用水溶液化学氧化聚合法合成了聚苯胺、苯胺共聚物及聚邻甲氧基苯胺,并对其性能与结构进行了测试、表征.实验表明:随着邻甲氧基苯胺含量的增加,聚合物的溶解性能有明显的改善,其氧化程度随之降低;以上三种聚合物均对马口铁表现出良好的防腐蚀性,其防腐蚀能力随氧化程度降低而降低;苯胺共聚物/环氧混合体系对马口铁也表现出优异的抗腐蚀性.     

聚苯胺/聚砜复合材料的制备及其超级电容性能

通过化学聚合法,制备出盐酸掺杂聚苯胺（PANI）,将其与聚砜（PSF）溶液混合,定量滴加到玻碳电极上制得PANI/PSF复合膜电极。 采用扫描电子显微镜、红外光谱以及X射线衍射对其结构和形貌进行表征。 根据循环伏安曲线、恒电流充放电曲线和电化学阻抗,研究了其作为电极的超级电容性能。 结果表明,多孔结构的PANI/PSF复合材料具有良好的电容性能,其比电容可达到497 F/g,并且该超级电容器具有较小的内阻和较好的循环稳定性。     

Enhanced sensitivity for biosensors: multiple functions of DNA-wrapped single-walled carbon nanotubes in self-doped polyaniline nanocomposites

A nanocomposite of poly(anilineboronic acid), a self-doped polyaniline, with ss-DNA-wrapped single-walled carbon nanotubes (ss-DNA/SWNTs) was fabricated on a gold electrode by in situ electrochemical polymerization of 3-aminophenylboronic acid monomers in the presence of ssDNA/SWNTs. We used this nanocomposite to detect nanomolar concentrations of dopamine and found that the sensitivity increased 4 orders of magnitude compared to the detection at an electrode modified with only poly(anilineboronic acid). For the first time, this work reports the multiple functions of the ss-DNA/SWNTs in the fabrication and biosensor application of a self-doped polyaniline/ss-DNA/SWNT nanocomposite. First, the ss-DNA/SWNTs acted as effective molecular templates during polymerization of self-doped polyaniline so that not only was the polymerization speed increased but also the quality of the polymer was greatly improved. Second, they functioned as novel active stabilizers after the polymerization, significantly enhancing the stability of the film. Furthermore, the ss-DNA/SWNTs also acted as conductive polyanionic doping agents in the resulting polyaniline film, which showed enhanced conductivity and redox activity. Finally, the large surface area of carbon nanotubes greatly increased the density of the functional groups available for sensitive detection of the target analyte. We envision that polyaniline with other functional groups as well as other conducting polymers may be produced for different targeted applications by this approach.     

Electrochemical Behavior of Methanol Influenced by Polyaniline Incorporated with Ferrocenesulfonic-carboxylic Acid

After the synthesis of polyaniline in the presence of ferrocenesulfoniccarboxylic acid, its influence on the electrochemical reaction of methanol was studied. The result indicates that the ferrocenyl in ferrocenesulfoniccarbexylic acid plays an important role in the electrocatalytic oxidation of methanol. CH3OH is adsorbed on PANI-Fc before its electrocatalytic oxidation. When the concentration of methanol is 2 mol/L, it begins to be oxidized. The effect of scan rate on the electrochemical reaction of methanol was also studied and 5 mV/s was favourable. It is another method to insert a metal catalyst in polyaniline without its electrodeposition.     

Copolypeptide-doped polyaniline nanofibers for electrochemical detection of ultratrace trinitrotoluene

This paper demonstrates a new electrochemical method for the detection of ultratrace amount of 2,4,6-trinitrotoluene (TNT) with synthetic copolypeptide-doped polyaniline nanofibers. The copolypeptide, comprising of glutamic acid (Glu) and lysine (Lys) units, is in situ doped into polyaniline through the protonation of the imine nitrogen atoms of polyaniline by the free carboxylic groups of Glu segments, resulting in the formation of polyaniline nanofibers of emeraldine salt. The free amino groups of Lys segments at the surface of nanofibers provide the receptor sites of TNT through the formation of charge-transfer complex between the electron-rich amino groups and the electron-deficient aromatic rings. Adsorptive stripping voltammetry results demonstrate that the poly(Glu-Lys)-doped nanofibers confined onto glassy carbon electrodes exhibit a remarkable enriching effect and thus sensitive electrochemical response to TNT with a linear dynamic range of 0.5-10 μM and a detection limit down to 100 nM. Moreover, other kinds of nitro compounds show different redox behaviors from TNT at the doped nanofibers, and thus do not interfere with the electrochemical detection of TNT. This study essentially offers a new and simple method for electrochemical detection of ultratrace TNT.     

β-萘磺酸掺杂聚苯胺纳米粒子的固相反应法制备及其表征

利用固相反应法制备了 β 萘磺酸掺杂的聚苯胺纳米粒子 ,并以红外光谱 (FTIR) ,扫描电子显微镜(SEM) ,透射电镜 (TEM) ,X 射线衍射 (XRD)以及粉末微电极等测试方法对其进行了表征 .结果表明 ,固相反应法合成的 β 萘磺酸掺杂聚苯胺粒子直径为 30～ 5 0nm ,聚苯胺分子链排列有序 ,晶化率较好 .粉末微电极的循环伏安测试表明 ,β 萘磺酸掺杂聚苯胺有较好的电化学活性 .     

循环伏安法的电扫描方式对苯胺聚合产物形貌影响的观察

在含有0.2 mol.L-1苯胺的0.5 mol.L-1H2SO4溶液中,以扫描速度50 mV.s-1,扫描电位为-0.1~0.9 V,采用循环伏安法(CV),在金属Ti基体上,通过控制扫描方式分别得到了颗粒状、纤维状及管-片状的苯胺聚合产物,分析了形成不同形貌聚苯胺的原因,并通过扫描电子显微镜(SEM)、循环伏安法和电化学阻抗谱(EIS)对不同形貌聚苯胺的结构和性能进行了表征.结果表明,不同形貌聚苯胺的形成是由于聚苯胺的成核及生长模式不同,而无论何种形貌的聚苯胺膜都具有很大的比表面积和良好的导电性能,其中,管-片状聚苯胺的膜层阻抗最小,导电性能最好.     

Formation Optimization and Electrocatalytic Properties of Platinum-Modified Polyaniline Films

The electrocatalytic properties of platinum particles incorporated into polyaniline films are investigated for oxidation of methanol in sulfuric acid electrolyte. It is found that the oxidation of methanol depends greatly on the nature of both polyaniline matrix and platinum particles which can be optimized by the electrochemical formation conditions, such as cycle numbers, deposition mode, and rotation rate.     

Nano-silicon/polyaniline composite for lithium storage

The nano-silicon connected by a nest-like polyaniline (PANi) was simply synthesized by a chemical polymerization process. The cycle stability and rate performance of the Si/PANi composite were greatly enhanced compared with the pristine nano-silicon. The improved electrochemical characteristics are attributed to the volume buffering effect as well as effective electronic conductivity of the nest-like polyaniline, and lower aggregation of the nano-silicon.