不同氧化剂制备聚苯胺纳米纤维研究

采用BPO和FeCl3·6H2O为氧化剂,以苯胺（An）为原料在界面体系下采用“无模板”的方法制备了聚苯胺纳米纤维。探讨了温度、氧化剂浓度对PANI结构及形貌的影响,研究发现FeCl3可同时起到氧化剂和掺杂剂的作用,且氧化剂的浓度直接影响到电导率的高低和聚苯胺的微观结构。以相对低廉、简单的生产工艺来合成出电导率高、且有一定长径比的聚苯胺（PANI）纳米纤维。     

一步法聚苯胺包覆镍纤维材料的制备及电性能研究

利用化学氧化法合成的聚苯胺对镍纤维进行包覆改性,拟改善镍纤维的导电性能。实验以苯胺、镍纤维为原料,研究了掺杂剂种类、掺杂剂浓度及搅拌速率对聚苯胺包覆镍纤维效果的影响,采用SEM、FT-IR对产物的形貌和结构进行分析,利用四探针电阻率测试仪测定了聚苯胺包覆镍纤维的导电性能。结果表明:在0.05mol/L的盐酸作为掺杂剂,搅拌速率为80r/min条件下,聚苯胺包覆镍纤维的包覆层均匀稳定,并得到最大的电导率,其最大值为1.52×10~3S/cm。     

聚苯胺/聚乳酸复合纳米纤维表面形貌对生物相容性的影响

外加电场作用下聚苯胺能够调节细胞附着、增殖、迁移和分化,在体液环境下发生脱掺杂会使聚苯胺基导电可降解纳米纤维电活性减弱,但在一定程度上仍能促进细胞的黏附、生长和增殖。本文选择酒石酸作为聚苯胺在等离子体处理后的聚乳酸纳米纤维表面原位聚合过程中的酸掺杂剂,考察酒石酸与苯胺摩尔比分别在1∶1, 1∶2和1∶4下不同形貌的聚苯胺/聚乳酸复合纳米纤维对生物相容性的影响。采用SEM、TEM和FTIR表征聚苯胺形貌及化学成分,接触角评价其润湿性,MTT、ALP和免疫荧光染色评价聚苯胺/聚乳酸复合纳米纤维生物相容性。结果表明,酒石酸与苯胺摩尔比在1∶1、1∶2和1∶4下的聚苯胺形貌分别为纳米颗粒状、纳米纤维状和纳米空心管状,聚苯胺附着在聚乳酸纳米纤维表面,不会对静电纺丝的多孔结构基体产生影响;聚苯胺/聚乳酸复合纳米纤维表面润湿性良好,有助于细胞的黏附和生长;纳米纤维状的聚苯胺对生物相容性的增强效果明显优于纳米颗粒状聚苯胺,而纳米空心管状结构的聚苯胺对生物相容性增强作用更佳。     

聚苯胺对电极在染料敏化太阳能电池的应用

通过软模板在FTO(导电玻璃)上化学浴沉积球状纳米聚苯胺和粉末聚苯胺,将以上两种对电极与无模板化学浴沉积聚苯胺对电极进行对比,并通过场发射扫描电子显微镜(FESEM)测试手段对这三种电极的表观形貌进行表征,对所制备三种电极进行了CV、EIS、Tafel、IV等电化学性能测试。结果表明:三种电极的表观形貌分别为球状结构聚苯胺、平整致密聚苯胺、蠕虫状聚苯胺,其中蠕虫状聚苯胺对电极因粗糙的表面和相对较大的厚度而具有较大的表面积,因此其催化活性位点也较多。而球状聚苯胺对电极则是三种电极中最有序的,规整的表面形貌使电极的导电性增加,加之其球状而产生的较大的表面积而使其光电转换效率在三种电极中最高,光电转换效率达到7.11%。     

不同酸掺杂聚苯胺形貌控制及对多巴胺检测研究

通过研究HCl、H3PO4和樟脑磺酸(CSA)掺杂对聚苯胺(PANI)纳米纤维形貌的影响得到其结构可控制备的规律。以掺杂PANI为电极材料对多巴胺(DA)进行差示脉冲伏安法测试,结果表明HCl和H3PO4掺杂的PANI对DA的电化学氧化活性较好,而H3PO4和CSA掺杂的PANI在DA检测中表现出较好的稳定性。     

聚苯胺复合膜的电性能研究

本文用红外光谱分别测试聚苯胺的本征态结构和掺杂态结构,分析聚苯胺掺杂前后分子结构的不同与导电性的关系。本工作以樟脑磺酸作掺杂剂,用溶液法把几种不同的聚合物与掺杂态聚苯胺共混,测其阀值为2.3wt％,并用扫描电镜照片对结果给以解释。     

磁性聚苯胺纳米纤维吸附性能的探究

以有机酸、粉煤灰磁珠为掺杂剂,过硫酸铵为氧化剂,采用氧化聚合的方法合成了磁性聚苯胺纳米纤维,对合成的磁性聚苯胺进行扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FT-IR)、紫外-可见光分光光度计(UV)、振动磁强计(VSM)、X-射线衍射仪(XRD)等表征,揭示了其形貌、结构、成分和磁性能,并使用磁性聚苯胺作吸附剂...     

磷酸二次掺杂聚苯胺纳米纤维的合成及其性能的研究

采用无模板直接混合法制备了硫酸一次掺杂聚苯胺,经氨水解掺杂得到本征态聚苯胺,然后在磷酸体系中对本征态聚苯胺进行二次掺杂。研究了不同的磷酸浓度,反应时间,搅拌时间等对二次掺杂聚苯胺电导率和产率的影响,得到磷酸二次掺杂聚苯胺合成的优化条件,并通过四探针测试仪、扫描电镜、红外光谱、紫外光谱以及电化学测试技术,对掺杂态聚苯胺进行了研究与表征。结果表明,室温下磷酸浓度为1 mol·L-1,搅拌反应24 h时,磷酸二次掺杂聚苯胺的电导率以及产率达到最大值,电导率为0.25 S·cm·1,产率达到138.7%。扫描电镜表征显示,磷酸二次掺杂可获得形貌良好的聚苯胺纳米纤维,其长度可达400~600 nm,且纤维直径均匀;紫外谱图和红外谱图表明磷酸能有效的掺杂到本征态聚苯胺中,改善其电导率及产率;电化学测试结果表明磷酸二次掺杂聚苯胺较一次掺杂聚苯胺有着更好的防腐蚀性能。     

聚（3，4-乙撑二氧噻吩）/樟脑磺酸复合材料的合成及其电化学性能

以樟脑磺酸(HCSA)为掺杂剂,FeCl3为氧化剂,通过化学氧化聚合合成了聚(3,4-乙撑二氧噻吩)/樟脑磺酸(PEDOT/HCSA)复合材料;采用FTIR和SEM对其结构和形貌进行了表征;探讨了掺杂剂与单体摩尔比、氧化剂用量和反应时间对产品导电性能的影响;分析了产品的电化学性能。结果表明,当n〔3,4-乙撑二氧噻吩(EDOT)〕:n(樟脑磺酸):n(氯化铁)=2:1:40,反应时间41 h时,复合材料具有良好的导电性能和电化学性能,电导率为10.4 S/cm,经150次充放电老化后比容量可保持在140 F/g左右,是一种潜在的超级电容器电极材料。     

纤维表面不同无机酸掺杂聚苯胺的制备及表征

采用改进的原位化学聚合法在涤纶纤维表面直接氧化生成聚苯胺薄膜。以盐酸、硫酸以及磷酸作为掺杂剂,过硫酸铵为氧化剂,探讨了掺杂过程中H+浓度对聚苯胺薄膜导电性能的影响,同时还利用衰减全反射法(ATR)以及场发射扫描电子显微镜(FE-SEM)对不同掺杂条件下的聚苯胺薄膜的红外光谱和形貌进行了分析和观察。     

Large‐scale synthesis of polyaniline nanofibers based on renewable resource molecular template

We report reproducible large‐scale synthesis of polyaniline (PANI) nanofibers up to 100 g scale via micelle mediated soft template approach. A unique built‐in amphiphilic azobenzenesulfonic acid based on renewable resource dopant was synthesized for large‐scale production of PANI nanofibres. The amphiphilic surfactant exists as 4.3 nm micelle in water and it self‐organized with aniline to form long cylindrical aggregates, which template for PANI nanofibers. The PANI nanofibers were found soluble in water and organic solvents and they were characterized by ¹H‐NMR, FT‐IR, and viscosity techniques. The mechanism of the PANI nanofiber formation was investigated by dynamic light scattering, scanning electron microscopy, and high resolution transmission electron microscopy. The width of the nanofibers was precisely controlled from 130–200 nm with length up to ～ 5 μm. The absorption spectroscopic analysis of nanofibers in water revealed that the large‐scale samples (10, 50, and 100 g) were found to posses expanded chain conformation compared to that of 1 g scale sample. The wide angle X‐ray diffraction patterns showed two new peaks at lower angles at d spacing of 25.5 and 13.6 Å corresponding to lamellar ordering of PANI chains followed by interdigitation of the amphiphilic dopant in the nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyaniline hollow microspheres constructed with their own self‐assembled nanofibers

Polyaniline (PANI) hollow microspheres constructed with their own nanofibers were prepared by inversed microemulsion polymerization associated with a template‐free method in the presence of β‐naphthalene sulfonic acid (β‐NSA) as the dopant. The hollow microspheres were 4.0–6.0 μm in outer diameter and 150–250 nm in shell thickness; they consisted of the nanofibers (20–30 nm in diameter and 150–250 nm in length). We propose that the coordination effect of the reversed emulsion and the dopant or dopant/aniline micelle might have been a driving force in the formation of the special microstructures/nanostructures, where the reversed microemulsion acted as a soft template in the formation of the microspheres and where NSA or the aniline/NSA micelle was regarded as a soft template in the formation of the nanofibers. The molar ratio of water to the aniline/NSA salt and ultrasonic irradiation were critical in the control of the formation yield and the diameter of the uniform microspheres. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3050–3054, 2006     

Electrochemical synthesis and optical properties of helical polyaniline nanofibers

Helical polyaniline (PANI) nanofibers were facilely synthesized via a direct electrochemical method without using any template in the presence of (1S)-(+)-camphor-10-sulfonic acid (d-CSA) or (1R)-(−)-camphor-10-sulfonic acid (l-CSA) as the dopant. The helical morphologies of the PANI nanofibers prepared from potentiostatic deposition were confirmed with SEM and TEM. The helical PANI nanofibers induced by d-CSA and l-CSA exhibited mirror-imaged circular dichroism spectra in the UV-vis range, indicating the stereochemical selectivity of the electrochemical polymerization. The colors and optical activities of these nanofibers can be maintained on an indium-tin oxide (ITO) coated electrode with a dedoping/redoping treatment. The optical activities of the helical PANI nanofibers reversibly varied with different oxidized forms, which were easily controlled by the different potentials applied to the nanofibers.     

Polyaniline self‐assembled with DTPA: Facilely tuned morphology and properties

The effects of pH profile and “soft template” during aniline chemical oxidative polymerization (COP) were investigated and evaluated simultaneously with diethylene triamine pentaacetic acid (DTPA) as a structural directing agent. Formation of PANI nanotubes and nanoparticles, smooth microspheres, and urchin‐like microspheres were illustrated by evaluating the pH profile during aniline COP while considering the “soft template” effects of DTPA. PANI nanosheets with two semicurled edges were found in the system producing nanotubes, which provides an evidence for the “curling mechanism” of PANI nanotube formation. With different pH profiles, chemical structures and aggregation structures of the as‐synthesized PANI micro/nanostructures are similar, whereas their conductivity, wettability, Cr (VI) adsorption, and electrochemical behaviors are distinct. The present study indicates that if properly conducted, pH profile adjustment is more effective than “soft template” to control the morphology and to optimize the performance of PANI micro/nanostructures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42403.     

High‐temperature oxidation of aniline to highly ordered polyaniline–sulfate salt with a nanofiber morphology and its use as electrode materials in symmetric supercapacitors

In this study, for the first time, aniline was oxidized by ammonium persulfate (APS) at higher temperatures without any protic acid, and APS acted as an oxidizing agent and a protonating agent. During the oxidation of aniline by APS, sulfuric acid formation occurred, and the sulfuric acid was incorporated into polyaniline (PANI) as a dopant. PANI–sulfate samples were characterized by IR spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. In this methodology, a highly ordered PANI–sulfate salt (H₂SO₄) with a nanofiber morphology was synthesized. Interestingly, a PANI base was also obtained with a highly ordered structure with an agglomerated netlike nanofiber morphology. PANI–H₂SO₄ was used as an electrode material in a symmetric supercapacitor cell. Electrochemical characterization, including cyclic voltammetry (CV), charge–discharge (CD), and impedance analysis, was carried out on the supercapacitor cells. In this study, the maximum specific capacitance obtained was found to be 273 F/g at 1 mV/s. Scan rate from cyclic voltammetry and 103 F/g at 1 mA discharge current from CD measurement. Impedance measurement was carried out at 0.6 V, and it showed a specific capacitance of 73.2 F/g. The value of the specific capacitance and energy and power densities for the PANI–H₂SO₄ system were calculated from CD studies at a 5‐mA discharge rate and were found to be 43 F/g, 9.3 W h/kg, and 500 W/kg, respectively, with 98–100% coulombic efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Redox Active Carbon Materials From Polyaniline: Plasma Carbonization,Heat Carbonization,and Preparation of Capacitors

Polyaniline (PANI) possessing a nanofiber structure is synthesized by a template-free method in the presence of camphor sulfonic acid. Nanostructured carbons were obtained by carbonization of PANI under heat treatment in argon flow at 1000°C. The nanofiber structure of the PANI was maintained after the carbonization. The carbon nanofiber based electrolytes were fabricated and characterized by electrochemical methods.     

Chemical synthesis and characterization of polyaniline nanofiber doped with gadolinium chloride

Gadolinium Chloride (GdCl₃) has been employed as dopant to synthesize conductive polyaniline (PANI) using chemical method. The resulting products were characterized using infrared spectroscopy, UV–vis spectra, scanning electron microscope, differential thermal analyzer, and X‐ray diffraction. It was found that Gd³⁺ can interact with PANI chains and induce changes on the properties of PANI. The addition of GdCl₃ could greatly increase electrical conductivity and crystalline degree of PANI. Changes in UV–vis and FTIR spectra show that there exists interaction between gadolinium ions and PANI chain. The effect of different proportions of ammonium persulfate on the properties of PANI was also discussed. When the molar ratios of GdCl₃ to aniline is 2 : 1 and ammonium persulfate to aniline is 1 : 1, the more uniform and regular PANI nanofiber can be prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 946–953, 2006     

Effect of Dopant on the Nanostructured Morphology of Poly (1-naphthylamine) Synthesized by Template Free Method

The study reports some preliminary investigations on the template free synthesis of a scantly investigated polyaniline (PANI) derivative—poly (1-naphthylamine) (PNA) by template free method in presence as well as absence of hydrochloric acid (HCl) (dopant), using ferric chloride as oxidant. The polymerization was carried out in alcoholic medium. Polymerization of 1-naphthylamine (NPA) was confirmed by the FT-IR as well as UV–visible studies. The morphology and size of PNA particles was strongly influenced by the presence and absence of acid which was confirmed by transmission electron microscopy (TEM) studies.     

Inverted emulsion polymerization route to polyaniline‐3D nanofiber network using sulfonated‐p‐cresol as novel dopant

Sulfonated‐p‐cresol (SPC) was used as novel dopant for the first time in the synthesis of polyaniline in 3D nanofiber networks (PANI‐3D). Polyaniline in 3D nanofiber network was prepared using organic solvent soluble benzoyl peroxide as oxidizing agent in presence of SPC and sodium lauryl sulfate (SLS) surfactant via inverted emulsion polymerization pathway. The influence of synthesis conditions such as the concentration of the reactants, stirring/static condition, and temperature etc., on the properties and formation of polyaniline nanofiber network were investigated. Polyaniline in 3D nanofiber network with 40–160 nm (diameter), high yield (134 wt % with respect to aniline used), and reasonably good conductivity (0.1 S/cm) was obtained in 24 h time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011