Preparation of polyaniline nanotubes array based on anodic aluminum oxide template

In this article, the highly ordered polyaniline (PANI) nanotubes array was prepared by in situ polymerization using anodic aluminum oxide (AAO) as template. Polymerization of aniline was confined in the one-dimensional nanochannel of AAO template. The aniline was adsorbed and polymerized preferentially on the pore walls of template. The structure of PANI nanotubes array was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), selected area electron diffraction (SAED) and dynamic force microscope (DFM). The results show that PANI nanotubes are synthesized successfully in the nanopores of template, the diameter and length of PANI nanotubes are closed to the pore diameter and thickness of AAO template, respectively, the arrangement of PANI nanotubes is very regular and uniform, the crystal form of PANI nanotubes is hexagonal, different from pseudo-orthorhombic crystal form of PANI bulk sample, and cell parameters a and b are 0.5008 nm. The change of crystal form is due to the confinement of AAO template, which makes the molecular chain of PANI arrange more ordered.     

Influence of dopant in the synthesis, characteristics and ammonia sensing behavior of processable polyaniline

Polyaniline (PANI) was synthesized by oxidative polymerization of aniline as well as aniline hydrochloride by ammonium persulfate in the presence of para-toluene sulfonic acid (PTSA). This helped in direct usage of the conducting PANI solution for film casting and use as a device for ammonia gas sensing. Viscosity change with applied shear rate was measured for both the polymers. Solid PANI powder was isolated from its tetrahydrofuran solution by using methanol as non-solvent. Thermogravimetric analysis investigated the thermal properties of the solid PANI salts. Elemental analysis of both PANI synthesized in presence of PTSA and PANI synthesized in presence of HCl and PTSA was investigated. A thin coherent film of both the conducting PANI were deposited on glass slides precoated with poly vinyl alcohol (PVA) crosslinked with maleic acid (MA) and was directly used in the sensor device. The morphology of the deposited films was analyzed by scanning electron micrograph. The films were further characterized by Attenuated total reflectance Fourier transformed infrared spectroscopy, ultra violet-visible spectroscopy and X-ray diffraction analyses. Finally, both the doped PANI films on MA crosslinked PVA coated glass slides were used to measure the conductivity and ammonia gas-sensing characteristics.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

Synthesis of high-performance one-dimensional polyaniline nanostructures using dodecylbenzene sulfonic acid as soft template

High-performance one-dimensional polyaniline (PANI) nanostructures, i.e. nanotubes and nanofibers were synthesized in the presence of dodecylbenzene sulfonic acid (DBSA) and hydrochloric acid (HCl) aqueous solution, with ammonium peroxydisulfate (APS) as oxidant. And the resulting PANI nanotubes possessed the diameters of 350-650 nm and length up to tens of micrometers and PANI nanofibers with diameters of 120-160 nm, respectively. Especially, the PANI nanotubes had a very uniform structure (nearly 100% in nanotubes) and the reaction yield was about 110% (compared to the quantity of aniline in the reaction). The formation mechanism of 1D PANI nanostructures was also proposed. The guide effect of the initial “soft-template” formed by aniline and DBSA was greatly controlled by its content and chemical structures.     

Effect of Pb2+ and Cu2+ as a codopant on the structure,morphology and conductivity of nanostructured polyaniline

Polyaniline (PANI) has been successively synthesized in aqueous diethylene glycol solution medium by chemical oxidative polymerization of aniline using ammonium peroxidisulfate [(NH₄)₂S₂O₈] as an oxidant in an aqueous solution of 0.5 M acetic acid (CH₃COOH) as a dopant. Polyaniline–lead (PANI–Pb) and polyaniline–copper (PANI–Cu) nanocomposites have been chemically prepared for the first time by oxidative polymerization of aniline in aqueous diethylene glycol/acetic acidic medium. The synthesized PANI and nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR). Conductivity measurements of the polymer and nanocomposites were performed using the four-probe technique. Morphology changes of the composites were investigated by scanning electron microscopy (SEM). PANI nanotubes were formed without added codopant, but when Pb(CH₃COO)₂ or Cu(CH₃COO)₂ was added as a codopant, the morphology of PANI obviously changed. The PANI–Cu and PANI–Pb nanocomposites exhibit higher conductivity than the PANI homopolymer, but the conductivity of the composites slightly decreased on increasing the metal concentrations.     

Electrochemical fabrication of polyaniline/multi-walled carbon nanotube composite films for electrooxidation of methanol

Polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) composite films were fabricated by electropolymerization of aniline containing well-dissolved MWNTs. The films can be used as catalyst supports for electro-oxidation of methanol. Cyclic voltammogram and Chronoamperogram results show that platinum particles deposited on PANI/MWNT composite films exhibit higher electrocatalytic activity towards methanol oxidation than that deposited on pure PANI films. The porous structure and electrical conductivity of PANI films has been significantly changed by introduction of MWNTs, higher surface areas of PANI/MWNT composites has been achieved therefore. It favors for platinum particles to be highly dispersed on the PANI/MWNT composite films and the better electrocatalytic activity of Pt/PANI/MWNT electrode is induced consequently.     

Studies on one-dimensional polyaniline (PANI) nanostructures and the morphological evolution

In this context, we studied the morphologies and morphology evolution of one-dimensional polyaniline (PANI) nanostructures during a wet chemical oxidation process via scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis methods. The results showed that the one-dimensional nanostructures of PANI followed a nucleation, agglomeration or self-growing processes, sequentially. Two distinctive morphologies were observed. One was that cylindrical nanotubes derived, most probably, from the self growing of the as-formed bubble-like ribbons. Another one, in comparison, was rectangular nanotubing structures stemmed from, apparently, a self-guided agglomerating or aggregating process of the as-formed primary nanoparticles, as confirmed unambiguously by both SEM and TEM observations. While the diameters of either individual or hyperbranched PANI nanotubes having a smooth surface were in the range of 250–1500 nm, the size of the rectangular nanotubings was ca. 600 nm.     

Synthesis of polyaniline nanofibrous networks with the aid of an amphiphilic ionic liquid

In this work, polyaniline (PANI) nanofibrous networks were prepared using ionic liquid (IL), 1-hexadecyl-3-methylimidazolium chloride (C16MIMCl), as a template through oxidative polymerization of aniline with ammonium persulfate. The resulting PANI was characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis, and FTIR. It was indicated that the as-prepared PANI was in the emeraldine form and its morphology strongly depended on the molar ratio of aniline/C16MIMCI. A possible mechanism for the formation of PANI nanofibrous networks was that the ordered micro-domains of the IL acted as template to direct the growth of the nanostructures.     

PANI/CeO_2纳米复合纤维材料的合成和表征

用水热法制备了纳米CeO2,并利用其氧化性通过原位聚合法制备出PANI/CeO2复合纳米纤维。采用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(FT-IR)等检测技术对复合材料的结构进行了表征。结果表明:复合材料两相间存在化学键合作用;酸浓度和无机纳米相影响了聚苯胺纤维结晶。当CPANI0.1mol/L,随着酸浓度的升高,PANI/CeO2的结构形态从球状逐渐发展成纤维状,CeO2粒子的粒径会影响聚苯胺结晶状态,粒径越小,越易形成结晶规整的纤维结构。     

Simultaneous synthesis of polyaniline nanorods and magnetite nanoparticles via self-assembly method

In this work, polyaniline (PANI) nanorods and magnetite (Fe₃O₄) nanoparticles have been synthesised by using ammonium persulphate as oxidant via in-situ chemical oxidative polymerisation of aniline in presence of excess of organic sulphonic acid. The resulting PANI/Fe₃O₄ nanocomposites materials were characterised using X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, vibrating sampling magnetometer and thermogravimetric analysis. Spectroscopic results indicated the successful formation of PANI/Fe₃O₄ nanocomposites. As obtained, PANI/Fe₃O₄ nanocomposites have Fe₃O₄ particle size in the range of 3.2–7?nm. Morphologies of PANI/Fe₃O₄ nanocomposites were found to be dependent on the molar ratio of aniline to organic acid. Under certain polymerisation conditions, PANI rods like structures were obtained. PANI/Fe₃O₄ nanocomposites have superparamagnetism and higher thermal stability.     

原位聚合 ( PSS/ PANI) n复合膜的静电层2层自组装

基于静电相互作用 , 从苯胺单体出发原位聚合、现场掺杂、层2层自组装制备多层聚苯乙烯磺酸钠( PSS) /聚苯胺 ( PANI) 复合膜。为了明确控制 PSS/ PANI复合膜纳米结构的因素 , 以紫外2可见 (UV2Vis) 光谱跟踪 PSS/ PANI复合膜的成膜过程 , 系统地研究了基片性质、 氧化剂用量及沉积时间等溶液因素对单个双层复合膜纳米结构的影响 , 得到了制备单个双层复合膜的较优条件。在此基础上变换苯胺单体浓度 , 制备了不同纳米结构的多层复合膜 ( PSS/ PANI) n, 并用原子力显微镜 (AFM) 、 扫描电镜 (SEM) 及椭偏仪等对该多层复合薄膜的形貌结构进行了表征。结果表明 , 通过控制沉积条件 , 每双层复合膜的厚度可控制在 40～100 nm , 电导率可达- 12. 675 mS·cm , 并且可制备增长均匀的 8 个双层的 ( PSS/ PANI) 8复合膜。热失重分析 ( TGA) 表明 , ( PSS/ PANI) n多层复合膜的热稳定性优于普通 PSS/ PANI复合膜。     

Interfacial synthesis of platinum loaded polyaniline nanowires in poly(styrene sulfonic acid)

Polyaniline-poly(styrene sulfonic acid)-platinum (PANI-PSS-Pt) composite is prepared through an interfacial polymerization route. The composite is obtained by incorporating Pt nanoparticles into conductive PANI matrix by the reduction of Pt⁴⁺ ions to Pt nanoparticles during the oxidative polymerization of aniline in PSS as medium. The interfacial synthesis offers the microenvironment for the growth of PANI nanostructures with simultaneous incorporation of Pt nanoparticles to result PANI-PSS-Pt nanocomposite. PANI-PSS-Pt nanocomposite is characterized by UV-Vis absorption spectroscopy, FTIR spectroscopy, scanning microelectronic microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS).     

高导电聚苯胺/纳米石墨微片复合材料的结构与性能

以天然可膨胀石墨(GN)为原材料,采用酸及快速热处理制备了膨胀石墨(EG),再将膨胀石墨置于超声波中制得了纳米石墨微片(NanoG),最后采用原位聚合法制备了聚苯胺/纳米石墨微片(PANI/NanoG)导电复合物。扫描电镜(SEM)显示纳米石墨微片长径为0.8μm～20μm,厚度为30nm～90nm。聚苯胺均匀覆盖在纳米石墨微片表面;透射电镜(TEM)揭示了纳米石墨微片的片层分散在复合物中并形成了导电网络;电性能测试表明,当纳米石墨微片含量为0.5%(质量分数,下同)时,复合物电导率达到107.3S/cm,其渗滤阈值达到0.1%,纳米石墨微片独特的结构(宽度/厚度的高比值)及在聚苯胺中的分散造就了复合物良好的导电性能。     

碳纳米管/聚苯胺复合材料的制备及电性能

利用超声波将多壁碳纳米管(CNTs)分散于苯胺盐酸溶液体系中,以过硫酸铵((NH4)2S2O8)为氧化剂,原位聚合法制备碳纳米管/聚苯胺纳米复合材料(CNTs/PANI)。采用扫描电子显微镜(SEM)、傅立叶变换红外光谱(FT-IR)、四探针电导率测试仪对复合材料进行表面观察、结构测定和电性能表征。结果表明,复合材料为核-壳结构,碳纳米管和聚苯胺间存在相互作用,其电导率随碳纳米管含量的增加而增加。     

Preparation and electrochemical characterization of polyaniline/activated carbon composites as an electrode material for supercapacitors

Polyaniline (PANI)/activated carbon (AC) composites were prepared by a chemical oxidation polymerization. To find an optimum ratio between PANI and AC which shows superior electrochemical properties, the preparation was carried out in changing the amount of added aniline monomers. The morphology of prepared composites was investigated by scanning electron microscopy (SEM) and transmission electron microscope (TEM). The structural and thermal properties were investigated by Fourier transform infrared spectra (FT-IR) and thermal gravimetric analysis (TGA), respectively. The electrochemical properties were characterized by cyclic voltammetry (CV). Composites showed a summation of capacitances that consisted of two origins. One is double-layer capacitance by ACs and the other is faradic capacitance by redox reaction of PANI. Fiber-like PANIs are coated on the surface of ACs and they contribute to the large surface for redox reaction. The vacancy among fibers provided the better diffusion and accessibility of ion. High capacitances of composites were originated from the network structure having vacancy made by PANI fibers. It was found that the composite prepared with 5 ml of aniline monomer and 0.25 g of AC showed the highest capacitance. Capacitance of 771 F/g was obtained at a scan rate of 5 mV/s.     

Investigation of solar-induced photoelectrochemical water splitting and photocatalytic dye removal activities of camphor sulfonic acid doped polyaniline-WO_3-MWCNT ternary nanocomposite

The camphor sulfonic acid doped polyaniline-WO_3-multiwall carbon nanotube(CSA PANI-WO_3-CNT)ternary nanocomposite was synthesized during in-situ oxidative polymerization and characterized by Fourier transform infrared(FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction(XRD), Field emission scanning electron microscopy(FESEM), X-ray photoelectron spectroscopy(XPS), Transmission electron microscopy(TEM), and Energy-dispersive X-ray spectroscopy(EDS). The application of CSA PANIWO_3-CNT ternary nanocomposite was investigated as the photocatalyst in the degradation of methylene blue dye(MB) and as the noble metal-free photoanode in photoelectrochemical water splitting under solar light irradiation. The degradation percentage of MB dye after 60 min illumination by CSA PANI-WO_3-CNT ternary nanocomposite reached 91.40% which was higher than that of pure WO_3(43.45%), pure CSA PANI(48.4%) and CSA PANI-WO_3 binary nanocomposite(85.15%). The photocurrent density of indium tin oxide(ITO)/CSA PANI-WO_3-CNT photoanode obtained 0.81 m A/cm~2 at 1.23 V vs. reversible hydrogen electrode under illumination which was 1.27, 2.13, and 4.26 times higher than that of the ITO/CSA PANI-WO_3(0.64 m A/cm~2), ITO/pure CSA PANI(0.38 m A/cm~2), and ITO/pure WO_3(0.19 m A/cm~2). Also,the applied bias photon-to-current efficiency(ABPE) of ITO/CSA PANI-WO_3-CNT was obtained 0.11%which showed two-fold, four-fold, and five-fold enhancements compared to the ITO/CSA PANI-WO_3,ITO/CSA PANI, and ITO/WO_3, respectively. The electrochemical impedance spectroscopy, as well as the Mott-Schottky results, confirmed the better photoelectrocatalytic activity of ITO/CSA PANI-WO_3-CNT in comparison with ITO/WO_3, ITO/CSA PANI, and ITO/CSA PANI-WO_3. The observed improvement in the photocatalytic and photoelectrocatalytic performances of WO_3 in the presence of CSA PANI is due to the formation of type-II heterojunction between WO_3 and CSA PANI which allows the separation of charge carriers easier and faster. On the other hand, MWCNT addition to the CSA PANI-WO_3 nanocomposite provided the conducting substrate for efficient interfacial charge separation as well as transferring.     

Synthesis, characterization and application in electrocatalysis of polyaniline/Au composite nanotubes

Polyaniline (PANI) nanotubes were successfully synthesized using the hydrothermal method via an in situ polymerization. In the process, a fibrillar complex of FeCl(3) and methyl orange (MO), acting as the reactive self-degraded templates, directed the growth of PANI on its surface and promoted the assembly into nanotubular structures. By introducing PANI nanotubes into Au colloid, Au nanoparticles (NPs) could be decorated onto the PANI nanotube surface through the electrostatic effect. The morphology of the nanotubes and the number of decorated Au NPs could be controlled effectively by adjusting the experimental conditions. The resulting products were characterized by transmission electron microscopy (TEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). In addition, the electrocatalytic activity of the composites towards the oxidation of NADH (nicotinamide adenine dinucleotide) was studied by immobilizing PANI/Au composites on the surface of a glassy carbon electrode (GCE).     

Preparation of gold/polyaniline/multiwall carbon nanotube nanocomposites and application in ammonia gas detection

Composites of multiwall carbon nanotubes (MWNTs), polyaniline (PANI), and gold nanoparticles were prepared by one pot synthesis. Based on the interaction between aniline monomers and MWNTs, aniline molecules were adsorbed and polymerized on the surface of MWNTs. The nanocomposites were characterized by transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoemission spectroscopy (XPS). The sensors based on Au/PANI/MWNT nanocomposites were tested for on-line monitoring of ammonia gas. The results show that the as-prepared sensors have superior sensitivity, and good repeatability upon repeated exposure to ammonia gas.     

Polyaniline/layered zirconium phosphate nanocomposites: secondary-like doped polyaniline obtained by the layer-by-layer technique

In the present work, nanocomposites of polyaniline (PANI) and layered alpha-Zr(HPO4)2 x H2O (alpha-ZrP) were prepared using two different approaches: (i) the in situ aniline polymerization in the presence of the layered inorganic material and (ii) the layer-by-layer (LBL) assembly using an aqueous solution of the polycation emeraldine salt (ES-PANI) and a dispersion of exfoliated negative slabs of alpha-ZrP. These materials were characterized spectroscopically using mainly resonance Raman scattering at four exciting radiations and electronic absorption in the UV-VIS-NIR region. Structural and textural characterizations were carried out using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The polymer obtained by the in situ aniline polymerization is located primarily in the external surface of the inorganic material although aniline monomers were intercalated between alpha-ZrP interlayer regions before oxidative polymerization. Through resonance Raman spectroscopy, it was observed that the formed polymer has semiquinone units (ES-PANI) and also azo bonds (-N=N-), showing that this method results in a polymer with a different structure from the usual "head-to-tail" ES-PANI. The LBL assembly of pre-formed ES-PANI and exfoliated alpha-ZrP particles produces homogeneous films with reproducible deposition from layer to layer, up to 20 bilayers. Resonance Raman (lambda0 = 632.8 nm) spectrum of PANI/ZrP LBL film shows an enhancement in the intensity of the polaronic band at 1333 cm(-1) (upsilonC-N*+) and the decrease of the band intensity at 1485 cm(-1) compared to bulk ES-PANI. Its UV-VIS-NIR spectrum presents an absorption tail in the NIR region assigned to delocalized free charge carrier. These spectroscopic features are characteristic of highly conductive secondary doped PANI suggesting that polymeric chains in PANI/ZrP LBL film have a more extended conformation than in bulk ES-PANI.     

Poly(aniline-co-m-aminobenzoic acid) deposited on poly(vinyl alcohol): Synthesis and characterization

In this work, we have deposited poly(aniline-co-m-aminobenzoic acid) on poly(vinyl alcohol) (PVA) by in situ polymerization. The polymerization was effected within maleic acid (MA) cross-linked PVA hydrogel. The copolymer was obtained by oxidative polymerization of aniline hydrochloride and m-aminobenzoic acid using ammonium persulfate as an oxidant. Instead of conventional solution polymerization, here synthesis was carried out on APS soaked MA cross-linked PVA (MA–PVA) film where the polymer was in situ deposited in its conducting form. The composite film was characterized by Fourier transform infra red (FT–IR) and ultraviolet visible (UV–VIS) spectroscopy and electrical measurements. Surface morphology of the composite films was studied by field emission scanning electron microscopy (FESEM). The variation of conductivity of the films was studied.