聚苯胺/纳米金复合材料

由于聚苯胺/纳米金复合材料不仅同时具有纳米金和聚苯胺原有的特异性能,而且两组分之间还存在着相互协同作用,极大地提升了聚苯胺基体的性能,从而表现出突出的固有电导性、优异的反应催化性和特殊的电荷传递性,因此成为近年来的研究热点。本文综述了聚苯胺/纳米金复合材料的最新研究进展：归纳了聚苯胺/纳米金复合材料的制备方法和各种方法的机理,简单介绍了复合材料在生物医学、传感器和微电子装置等方面的应用,展望了今后复合材料研究的方向。     

不同质子酸掺杂对银/聚苯胺纳米复合材料结构和导电性的影响

利用紫外光作为辅助条件,在反胶束体系中采用一步双原位法合成了硝酸(HNO3)、对甲基苯磺酸(TSA)和5-磺基水杨酸(SSA)掺杂的银/聚苯胺(Ag/PANI)纳米复合材料.通过对复合材料进行红外光谱(FTIR)、紫外光谱(UV-Vis)、扫描电镜(SEM)、X射线衍射(XRD)和导电性能的测试,研究了不同质子酸对Ag/PANI纳米复合材料结构、形貌和导电性能的影响.测试结果表明,3种酸掺杂制备的Ag/PANI纳米复合材料均为聚苯胺包覆银粒子的核-壳结构.不同的质子酸掺杂会对Ag/PANI纳米复合材料的电性能有重要影响.在3种酸掺杂的复合材料中,TSA掺杂的复合材料的电导率最佳,为215.14 S·cm-1.     

一步法合成聚苯胺/十二烷基苯磺酸钠超疏水复合材料

在阴离子表面活性剂十二烷基苯磺酸钠(SDBS)体系中,采用一步法制得聚苯胺/SDBS超疏水复合材料.利用场发射扫描电子显微镜(FESEM)观察产物形貌并测定其元素组成.通过傅里叶变换红外光谱仪、紫外-可见光谱仪、X射线衍射等对其结构进行表征,用视频接触角测量仪测定材料的亲疏水性.考察SDBS浓度和溶液酸度对产物形貌及疏水性能的影响,探讨疏水机理.结果表明:在pH=1-9,SDBS浓度大于0.016 mol?L-1条件下,所制备复合材料的水接触角大于150°,SDBS掺杂使得苯胺单体的转化率高达98%.两亲分子SDBS亲水磺酸基与聚苯胺主链上的亚胺基不仅存在静电引力,而且能形成磺酰胺键,聚苯胺主链间又以氢键相互连接,SDBS分子的疏水烃基有序排列朝向聚苯胺主链外侧,从而组装形成具有微纳结构的聚苯胺/SDBS超疏水复合材料.本文结果有利于更好地理解聚苯胺/SDBS超疏水性复合材料的形成机理,对超疏水材料的设计提供新思路.     

石墨烯/聚苯胺复合材料的制备及其电化学性能

以苯胺和氧化石墨烯(GO)为原料, 采用电化学方法制备了石墨烯/聚苯胺(GP)复合材料. 利用X射线衍射(XRD)、扫描电镜(SEM)、拉曼(Raman)光谱、X射线光电子能谱分析(XPS)对其结构、微观形貌进行了表征,并对复合材料电化学性能进行了测试. 结果表明, 复合材料保持了石墨烯的基本形貌, 聚苯胺颗粒均匀地分散在石墨烯表面, 复合材料在500 mA·g^-1的电流密度下比电容达到352 F·g^-1, 1000 mA·g^-1下比电容为315 F·g^-1, 经过1000 次的充放电循环后容量保持率达到90%, 远大于石墨烯和聚苯胺单体的比电容. 复合材料放电效率高, 电解质离子易于在电极中扩散和迁移.     

聚苯胺/介孔碳纳米线复合电极材料的制备和性能

以介孔碳纳米线为基体, 通过电化学方法制备了新型聚苯胺/介孔碳纳米线(PANI/MCFs)复合材料, 采用SEM和TEM等手段对样品的结构和形貌进行了表征. 结果表明, 聚苯胺均匀附在介孔碳纳米线表面, 并填充到纳米线介孔孔道中. 将复合材料组装成三电极体系超级电容器, 用循环伏安、 恒流充放电和交流阻抗等方法对材料的电化学性能进行了测试. 结果显示, 在1 mol/L H₂SO₄溶液中, 复合材料的比电容达到391 F/g, 其循环稳定性也得到显著提高.     

三维还原氧化石墨烯/聚苯胺复合材料的制备及其超级电容性能

以制备的氧化石墨凝胶和聚苯胺纳米线为原料, 将二者按一定的质量比进行混合超声分散, 再以混合分散液为前驱体采用一步水热法制备得到三维还原氧化石墨烯(RGO)/聚苯胺(PANI) (RGP)复合材料, 采用扫描电镜(SEM), 透射电镜(TEM), X射线衍射(XRD), 傅里叶变换红外(FT-IR)光谱, X射线光电子能谱(XPS)和电化学测试等分析研究了复合材料的形貌、结构和超级电容性能. 结果表明, 复合材料既保持了还原氧化石墨烯的基本形貌, 又能使聚苯胺较好地镶嵌在还原氧化石墨烯的网状结构中; 且当氧化石墨与聚苯胺的质量比为1:1时复合材料在0.5 A·g^-1电流密度下比电容可高达758 F·g^-1, 即使在大电流密度(30 A·g^-1)下其比容量仍高达400 F·g^-1,在1A·g^-1电流密度下循环1000次后比容量保持率为86%, 表现出了良好的倍率性能和循环稳定性, 其超级电容性能远优于单纯的还原氧化石墨烯和聚苯胺, 其优异的超级电容性能可归咎于二者的相互协同作用.     

MnO_2/聚苯胺复合材料的电化学电容

以P123为模板剂,软模板法制备出纳米MnO2.酸性条件下引入苯胺并聚合,得到了MnO2/聚苯胺复合材料.X射线衍射(XRD)、红外光谱(IR),扫描电子显微镜(SEM)表征观察样品的结构、形貌.循环伏安、交流阻抗、恒电流充放电等测试MnO2/聚苯胺电极的电化学性能.结果表明:引入苯胺改变了样品纳米MnO2的形貌.MnO2/聚苯胺电极比容量高达190.8F·g-1,500次循环电极比容量仅衰减4.7%,库仑效率均保持在97%以上.     

新型质子酸掺杂聚苯胺的合成及其电化学电容行为

用化学氧化聚合法制得了草酸掺杂聚苯胺(H2C2O4-PANI)和柠檬酸掺杂聚苯胺(C6H8O7-PANI),并与盐酸掺杂聚苯胺(HCl-PANI)做了对比研究.用红外光谱(FT-IR)、X射线衍射(XRD)和透射电镜(TEM)对掺杂聚苯胺的结构和形貌进行了表征.用循环伏安,恒流充放电和交流阻抗测试对材料在1 mol/L HCl溶液中的电化学电容行为进行了研究.结果表明:3种酸掺杂的聚苯胺具有不同的空间结构,电化学性能也有差异.与盐酸和柠檬酸掺杂的聚苯胺相比,草酸掺杂制备的聚苯胺表现出更优良的电化学电容行为,单电极比电容可达670 F/g.     

聚苯胺/碳化钨导电复合材料的合成

以苯胺和过硫酸胺为原料,采用原位聚合方法合成了聚苯胺/碳化钨(PANI/WC)导电复合材料。研究了反应体系中碳化钨的含量对复合材料电导率的影响,确定了较佳的聚合条件,并且通过FT-IR、XRD、XPS和DSC-TGA等手段对复合材料的结构和性能进行了表征和分析。结果表明:碳化钨(WC)的加入提高了聚苯胺的电子导电性能,复合材料中聚苯胺组分为无定型,WC的晶型在反应前后并未发生变化,复合材料的热稳定性好并且质子化程度更高。     

聚苯胺共价接枝碳纳米管复合材料的制备及其超电容性能的研究

以氨基化的碳纳米管为基体, 通过低温原位聚合的方法将聚苯胺共价接枝于碳纳米管表面, 通过透射电镜(TEM)、X射线衍射(XRD)、紫外可见光(UV-vis)、傅里叶红外(FT-IR)、拉曼(Raman)及电化学方法对复合材料进行了表征. 结果表明通过低温原位聚合的方法可以使聚苯胺均匀接枝于碳纳米管表面. 电化学测试结果表明, 碳纳米管共价接枝聚苯胺作为超级电容器材料在0.5 A/g条件下聚苯胺的电容贡献值为754.8 F/g, 同时其倍率性能以及循环稳定性方面都明显优于聚苯胺非共价修饰的碳纳米管复合材料.     

Preparation of highly conductive, self-assembled gold/polyaniline nanocables and polyaniline nanotubes

One-dimensional gold/polyaniline (Au/PANI-CSA) coaxial nanocables with an average diameter of 50-60 nm and lengths of more than 1 mum were successfully synthesized by reacting aniline monomer with chlorauric acid (HAuCl(4)) through a self-assembly process in the presence of D-camphor-10-sulfonic acid (CSA), which acts as both a dopant and surfactant. It was found that the formation probability and the size of the Au/PANI-CSA nanocables depends on the molar ratio of aniline to HAuCl(4) and the concentration of CSA, respectively. A synergistic growth mechanism was proposed to interpret the formation of the Au/PANI-CSA nanocables. The directly measured conductivity of a single gold/polyaniline nanocable was found to be high (approximately 77.2 S cm(-1)). Hollow PANI-CSA nanotubes, with an average diameter of 50-60 nm, were also obtained successfully by dissolving the Au nanowire core of the Au/PANI-CSA nanocables.     

聚苯胺分子印迹膜电化学传感器检测氯霉素

以苯胺为功能单体和交联剂,氯霉素(chloramphenicol,CAP)为模板分子,采用电化学聚合法(循环伏安法)在金电极上合成了对CAP具有快速响应能力的聚苯胺分子印迹膜;结合差示脉冲伏安法建立了针对氯霉素的检测方法,并将所制备的聚苯胺分子印迹膜用作电化学传感器以测定氯霉素眼药水中的氯霉素.结果表明,所制备的聚苯胺分子印迹膜具有制备简单、响应快速、灵敏度高、再生性能良好等特点;其对氯霉素眼药水中的氯霉素的检测结果令人满意,有望用于实际样品中氯霉素的检测.     

Pyridinium chlorochromate oxidation route to polyaniline

In this work, for the first time, pyridinium chlorochromate is used as an oxidizing agent inorder to oxidize aniline to polyaniline salts via an aqueous polymerization pathway in the presence of protic acids such as sulfuric, nitric, hydrochloric and phosphoric acid. The polymer samples were characterized by infrared, electronic absorption spectral, elemental analysis, conductivity, density and water absorption measurements. The results of the polyaniline salts prepared by pyridinium chlorochromate as an oxidizing agent were compared with that of the polyaniline salt prepared by ammonium persulfate. Generally, aniline is oxidized using ammonium persulfate as an oxidizing agent, which is unstable. In this work, pyridinium chlorochromate is used to oxidize aniline to polyaniline salt and the polymerization reaction could be completed in 30 min. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis of core‐shell silver–polyaniline nanocomposites by gamma radiolysis method

Core‐shell silver (Ag)–polyaniline (PAni) nanocomposites have been synthesized by the in‐situ gamma radiation‐induced chemical polymerization method. Aqueous solution of aniline, a free‐radical oxidant, and/or silver metal salt were irradiated by γ‐rays. Reduction of the silver salt in aqueous aniline leads to the formation of silver nanoparticles which in turn catalyze oxidation of aniline to polyaniline. The resultant Ag‐PAni nanocomposites were characterized by using different spectroscopy analyses like X‐ray photoelectron, UV–visible, and infrared spectroscopy. The optical absorption bands revealed that the bands at about 400 nm are due to the presence of nanosilver and the blue‐shifted peak at ～ 555 nm is due to the presence of metallic silver within the PAni matrix. X‐ray diffraction pattern clearly indicates the broad amorphous polymer and the sharp metal peaks. Scanning electron microscopy and transmission electron microscopy of the nanocomposite showed a uniform size distribution with spherical and granular morphology. Thermogravimetric analysis revealed that the composites have a higher degradation temperature than polyaniline alone. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5741–5747, 2007     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

Fabrication and characterization of core/shell structured TiO2/polyaniline nanocomposite

A novel core/shell structured TiO(2)/polyaniline nanocomposite was fabricated by grafting aniline on aminobenzoate monolayer that is chemically adsorbed on the TiO(2) nanocrystal surface. The formation and nanostructure of the nanocomposite were investigated by FT-IR and UV-Vis spectra, TEM, FE-SEM, and TG-DTA analysis. Adsorption of aminobenzoate on the TiO(2) surface is an effective method to obtain the uniform nanocomposite. The thickness of polyaniline layer coating on the TiO(2) nanocrystal surface can be controlled in a range of 2-5 nm by this method. A photoelectrochemical study was carried out on the TiO(2)/polyaniline nanocomposite, and found that polyaniline in the nanocomposite acted as a visible-light sensitizer in a photoelectrochemical reaction. The sensitization effect increased with increasing binding strength between polyaniline and TiO(2). A dye-sensitized solar cell with a short circuit current density of 0.19 mA/cm(2) and an open circuit voltage of 0.35 V was fabricated by using the TiO(2)/polyaniline nanocomposite film as a sensitized electrode.     

Nanocomposites of Sulfonic Polyaniline Nanoarrays on Graphene Nanosheets with an Improved Supercapacitor Performance

A new nanocomposite, poly(aniline‐co‐diphenylamine‐4‐sulfonic acid)/graphene (PANISP/rGO), was prepared by means of an in situ oxidation copolymerization of aniline (ANI) with diphenylamine‐4‐sulfonic acid (SP) in the presence of graphene oxide, followed by the chemical reduction of graphene oxide using hydrazine hydrate as a reductant. The morphology and structure of PANISP/rGO were characterized by field‐emission (FE) SEM, TEM, X‐ray photoelectron spectroscopy (XPS), Raman, FTIR, and UV/Vis spectra. The electrochemical performance was evaluated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. The PANISP/rGO nanocomposite showed a nanosized structure, with sulfonic polyaniline nanoarrays coated homogeneously on the surface of graphene nanosheets. This special structure of the nanocomposite also facilitates the enhancement of the electrochemical performance of the electrodes. The PANISP/rGO nanocomposite exhibits a specific supercapacitance up to 1170 F g^?1 at the current density of 0.5 A g^?1. The as‐prepared electrodes show excellent supercapacitive performance because of the synergistic effects between graphene and the sulfonic polyaniline copolymer chains.     

乳液聚合法制备纳米金/聚苯乙烯复合粒子

以氯金酸为前驱体,十二烷基硫醇和硼氢化钠分别作为稳定剂和还原剂,采用相转移法制备了单分散的金纳米粒子.将金纳米粒子通过乳液聚合的方法制备了纳米金/聚苯乙烯复合粒子.通过紫外-可见吸收光谱(UV-Vis)研究了纳米金和纳米金/聚苯乙烯复合粒子的光吸收特性,使用傅立叶变换红外光谱(FT-IR)、X射线衍射(XRD)、透射电子显微镜(TEM)和动态光散射(DLS)对产物的组成、晶体结构、形貌、以及粒径进行了表征.结果表明,复合粒子为粒径分布较窄的球形,其中的金纳米粒子为面心立方结构.热失重分析(TGA)说明制备的纳米金/聚苯乙烯复合粒子具有很好的热稳定性.     

EMI shielding and microwave absorption behavior of Au‐MWCNT/polyaniline nanocomposites

Electrically conducting Au‐multiwalled carbon nanotube/polyaniline (Au‐MWCNT/PANi) nanocomposites were synthesized by two different ways: (1) by direct mixing of MWCNT/PANi and Au nanoparticles (Au‐MWCNT/PANi‐1) and (2) by in situ polymerization of aniline in the presence of both MWCNTs and Au nanoparticles (Au‐MWCNT/PANi‐2). The higher electrical conductivity of Au‐MWCNT/PANi‐2 compared with the other samples (PANi, MWCNT/PANi, Au‐MWCNT/PANi‐1) is supported by the red shifts of the UV‐vis bands (polaron/bipolaron), the high value of the –NH+= stretch peak (Fourier transform infrared spectroscopy studies), the high % crystallinity (X‐ray diffraction analysis) and more uniform dispersion of the Au NPs in the material. The performance of the samples in electromagnetic interference (EMI) shielding and microwave absorption was studied in the X‐band (8–12 GHz). For all the samples, absorption was the dominant factor contributing toward the EMI shielding. Au‐MWCNT/PANi‐2 showed the best performance with a total shielding effectiveness of ?16 dB [averaged over the X‐band (GHz)] and a minimum reflection loss of ?56.5 dB. The higher dielectric properties resulting from the heterogeneities because of the presence of nanofillers and the high electrical conductivity lead to the increased EMI shielding and microwave absorption. The results show the significance of both Au nanoparticles and method of synthesis on the EMI shielding performance of MWCNT/PANi composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis of gold–polyaniline nanocomposites by complexation

Complexation synthesis methods have been examined in the preparation of nanogold–polyaniline systems. This extends work previously reported on the use of a spontaneous redox coupling of aniline polymerization to the reduction of a gold salt added to the monomer and mixed initially at the molecular level. The extension involves the addition of an additional reducing agent in the form of borohydride. The end product of the nanoparticle Au–PANI composite is very much a function of the borohydride : Au and N : Au ratios used in the synthesis. The size of the resulting gold particles can be directly tuned in the diameter range 2–10 nm by adjusting the borohydride : Au ratio used. Thorough characterization of the structures of the composites has been undertaken. Copyright © 2016 John Wiley & Sons, Ltd.