Preparation and Characterization of Polypyrrole/TiO2 Coaxial Nanocables

Summary: We demonstrate in this communication that large‐scale coaxial nanocables of polypyrrole (PPy)/TiO₂ can be obtained via three steps: (1) synthesis of TiO₂ nanofibers by electrospinning; (2) physical adsorption Fe³⁺ oxidant on the surface of TiO₂ nanofibers; (3) followed by polymerization of pyrrole (from vapor) on the surface of TiO₂ nanofibers. During the synthesis, the PPy formed on TiO₂ nanofibers as a template and formed PPy/TiO₂ coaxial nanocables. TEM image proved that PPy (20 nm thickness) covered the surface of TiO₂ nanofibers. Fourier‐transform infrared (FTIR), X‐ray photoelectron spectra (XPS), and X‐ray diffraction patterns (XRD) characterized the chemical structure of the coaxial nanocables. Surface photovoltage spectroscopy (SPS) revealed the surface properties of the PPy/TiO₂ coaxial nanocables.

TEM image of individual PPy/TiO₂ coaxial nanocable.     

Synthesis and characterization of polypyrrole nanofibers with different dopants

Nanostructures of polypyrrole (PPy) were synthesized in the presence of different dopants including hydrochloric acid (HCl), ferric chloride (FeCl₃), p‐toluene sulfonic acid (p‐TSA), camphor sulfonic acid (CSA), and polystyrene sulfonic acid (PSSA), using a simple interfacial oxidative polymerization method. The method is a reliable non‐template approach with relatively simple instrumentation, ease of synthesis, and economic viability for synthesizing PPy nanostructures. Morphology of synthesized PPy structures was investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which indicate the formation of one‐dimensional (1D) nanofibers with average diameter of 75–180 nm. Energy dispersive spectrum (EDS) of the PPy nanofibers indicates the attachment of the dopants to the PPy backbone; the fact is further confirmed by the Fourier transform infrared (FTIR) spectra of PPy nanostructures. Thermal stabilities of the nanostructures explored using thermal gravimetric analysis (TGA) follow the order PPy‐p‐TSA > CSA > HCl > FeCl₃ > PSSA. It is noticed that the electrical conductivity (EC) of PPy nanostructures depends upon the nature of dopant (PPy‐p‐TSA > CSA > HCl > FeCl₃ > PSSA), PPy‐p‐TSA nanofibers showing the highest EC of 6 × 10^?2 Scm^?1. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of polypyrrole micro/nanofibers via a self-assembly process

Novel polypyrrole (PPy) micro/nanofibers were synthesized via a self-assembly process by using 4-hydroxy-3-[(4-sulfo-1-naphthalenyl) azo]-1-naphthalenesulfonic acid (Acid Red B) as dopant and ferric chloride (FeCl₃) as oxidant. Experimental conditions, including the concentration of the dopant, reaction temperature and stirring state have been investigated for their influences on the morphology of the synthesized PPy micro/nanofibers. The products were characterized by scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared spectroscopy. The formation mechanism of micro/nanofibers was studied. It is believed that the micelles formed by the dopant and pyrrole monomer act as templates during the synthesis process. Two functions of aggregation and synthesis are proposed in the reaction system simultaneously, and the morphologies of micro/nanofibers are the co-operations of these two functions. The maximum conductivity value of the PPy micro/nanofibers was 8.56 S cm^?1     

In situ polymerization and morphology of polypyrrole obtained in water‐soluble polymer templates

Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl₃ as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen ¹H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Facile one‐step synthesis of electromagnetic functionalized polypyrrole/Fe3O4 nanotubes via a self‐assembly process

This article reports a simple self‐assembly process for facile one‐step synthesis of novel electromagnetic functionalized polypyrrole (PPy)/Fe₃O₄ composite nanotubes using p‐toluenesulfonic acid (p‐TSA) as the dopant and FeCl₃ as the oxidant. The key trick of the present method is to use FeCl₃ as the oxidant for both PPy and Fe₃O₄ in the same time to synthesize PPy/Fe₃O₄ composite nanotubes in one‐step. This facile one‐step method is much simpler than the conventional approach using the Fe₃O₄ nanoparticles as the additives. Compared to the similar composites synthesized using the conventional method, the as‐prepared PPy‐p‐TSA/Fe₃O₄ composite nanotubes using the facile one‐step self‐assembly process show much higher room‐temperature conductivity. Moreover, the composite nanotubes display interesting ferromagnetic behavior. The electrical properties of the PPy‐p‐TSA/Fe₃O₄ composite nanotubes are dominated by the amount of FeCl₃ while their magnetic properties are controlled by the amount of FeCl₂. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 320–326, 2010     

Synthesis and Characterization of Polyvinylferrocene/Polypyrrole Composites

Conducting polymer composites of polyvinylferrocene and polypyrrole (PVF/PPy) were synthesized chemically by the in situ polymerization of pyrrole in the presence of PVF using FeCl₃ as oxidant. Acetic (CH₃COOH) and boric (H₃BO₃) acids were used as the synthesis medium. Effects of the synthesis medium on the properties of the PVF/PPy composite were investigated. The PVF/PPy composites and homopolymers were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and magnetic susceptibility techniques. Conductivity measurements were performed using the four‐probe technique. We found that the conductivities of PVF/PPy‐H₃BO₃ (1.19 S cm^?1) and PVF/PPy‐CH₃COOH (4.5×10^?1 S cm^?1) increased relative to those of the homopolymers of PPy‐H₃BO₃ (2.1×10^?2 S cm^?1) and PPy‐CH₃COOH (1.2×10^?2 S cm^?1) due to the interaction of PVF with the pyrrole moiety. The stability of all homopolymers and composites were investigated by thermogravimetric analysis and by conductivity measurements during heating‐cooling cycles. There was a small drop in conductivity caused by the annealing of PVF/PPy composites at 70°C. The conductivity of all samples increased with temperature and exhibited stable electrical behavior with increasing temperature. TGA analysis of samples showed that the composites were more stable than the homopolymers or PVF separately. The magnetic susceptibility values of samples were negative, except for PVF/PPy‐H₃BO₃. Morphology changes of the composites investigated by scanning electron microscopy (SEM), attributed to synthesis conditions, have a significant effect on their conductivity.     

Preparation of polypyrrole-coated silicon nanoparticles

Silicon (Si) nanoparticles were stabilized by sodium dodecyl sulfate and poly(N-vinylpyrrolidone) in water, and coated with polypyrrole (PPy) via in situ polymerization of pyrrole with FeCl₃. TEM images revealed that the Si nanoparticles were successfully coated with PPy (average thickness, ∼2 nm). The Li/PPy-coated Si electrode exhibited improved discharge capacities, compared to that of a reported Li/pure Si electrode, even though the capacity fading problem caused by large-scaled crumbling of the electrode was not overcome.     

The development of conductive composite surfaces by a diffusion-limited in situ polymerization of pyrrole in sulfonated polystyrene ionomers

Electrically conductive composite surfaces were prepared by a diffusion-controlled in situ polymerization of pyrrole in the surface layer of sulfonated polystyrene ionomer films. Premolded films of the ionomer sulfonic acid derivatives were sequentially immersed in aqueous solutions of pyrrole and FeCl₃, and polymerization occurred only where both the monomer and the oxidant were present. The penetration of the polypyrrole (PPy) into the film was controlled by varying the immersion time in the monomer solution. The amount of PPy produced depended on the immersion time of the film in the monomer and the degree of sulfonation of the ionomer. Surface conductivities of 10⁻⁴-10⁻¹ S/cm were achieved with PPy concentrations from 2 to 22 wt % and composite layers as thin as 15 μm. Intermolecular interactions occurred between PPy and the ionomer by proton transfer. Incorporation of PPy also increased the tensile strength of the ionomer film, significantly increased its modulus above T_g, and inhibited melt flow. © 1997 John Wiley & Sons, Inc.     

Conducting core‐sheath nanofibers for electroactive shape‐memory applications

Conducting nanofibers coated with polypyrrole (PPy) and poly(3‐hexylthiophene) (P3HT) exhibiting core‐sheath structures were prepared by vapor‐phase polymerization of the conducting polymers on electrospun polyurethane nanofibers. The synthesis of the conducting polymers was confirmed by Fourier transform infrared spectroscopy and energy‐disperse X‐ray spectroscopy. The surfaces of the PPy‐coated nanofibers were slightly rough, while very smooth and regular surfaces were observed in the case of the P3HT‐coated nanofibers. The initial polymerization rate of PPy was higher than that of P3HT. In addition, the electrical conductivities of the core‐sheath structured nanofiber webs of both types increased with polymerization time. The maximum sheet conductivity of the PPy and P3HT‐coated nanofiber webs was 5 × 10^?3 S/cm and 1 × 10^?2 S/cm, respectively. The webs of the conducting core‐sheath structured nanofibers were effective in generating sufficient electrical heating necessary for harnessing these materials for electroactive shape‐memory‐based applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Novel electromagnetic functionalized γ‐Fe2O3/polypyrrole composite nanostructures with high conductivity

In general, the conductivity of polypyrrole (PPy) is reduced by addition of magnetic nanoparticles as the additives owing to insulating effect of magnetic nanoparticles. In this article, novel electromagnetic functionalized PPy composite nanostructures were prepared by a template‐free method associated with γ‐Fe₂O₃ nano‐needles as the hard templates in the presence of p‐toluene‐sulfonic acid (p‐TSA) and FeCl₃·6H₂O as the dopant and oxidant, respectively. It was found that the molar ratio of γ‐Fe₂O₃ to pyrrole monomer represented by [γ‐Fe₂O₃]/[Py] ratio strongly affected the morphology and the conductivity of the γ‐Fe₂O₃/PPy composite nanostructures. A growth mechanism for the composite nanostructures was proposed based on the variance of the morphology with the [γ‐Fe₂O₃]/[Py] ratio. Compared with previously reported γ‐Fe₂O₃/PPy composites, the as‐prepared novel composite nanostructures showed much higher conductivity (up to ～50 times higher). Moreover, the synthesized γ‐Fe₂O₃/PPy composite nanostructures displayed ferromagnetic behavior with a high coercive force. Explanations for these interesting observations were made in terms of the magnetic interaction between ferromagnetic γ‐Fe₂O₃ nano‐needles and spin‐polaron of PPy nanotubes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4446–4453, 2009     

Frequency‐dependent conductivity of interpenetrating polymer network composites of polypyrrole–poly(vinyl acetate)

The frequency‐dependent conductivity of interpenetrating polymer network composites of polypyrrole (PPy) and poly(vinyl acetate) (PVAc) synthesized by FeCl₃‐impregnated PVAc films being dipped into solutions of pyrrole in water was investigated over a frequency range of 100 Hz to 2 MHz and a temperature range of 110–300 K. For specimens with a PPy content less than the percolation threshold, the quantum mechanical tunneling of electrons was the conduction mechanism. For specimens with a higher PPy content, correlated barrier hopping of electrons appeared to be operative. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1935–1941, 2001     

Ammonia Gas Sensor Using Polypyrrole‐Coated TiO2/ZnO Nanofibers

Highly porous polypyrrole (PPy)‐coated TiO₂/ZnO nanofibrous mat has been successfully synthesized. The core TiO₂/ZnO nanofibers have an average diameter of ca. 100 nm and the shell of ultrathin PPy layer has a thickness of ca. 7 nm. The NH₃ gas sensor using the as‐prepared material exhibited a fast response over a wide dynamic range and high sensitivity with a detection limit of 60 ppb (S/N=3). Compared to conventional pristine PPy film, the improved performance in NH₃ detection can be attributed to the free access of NH₃ to PPy and a minimized gas diffusion resistance through the ultrathin PPy layer.     

Effects of FeCl3 as oxidizing agent on the conduction mechanisms in polypyrrole (PPy)/pc–ZnO hybrid heterojunctions grown by oxidative chemical vapor deposition

P‐type polypyrrole (PPy) films are deposited on glass and on n‐type polycrystalline ZnO (pc–ZnO) substrates by oxidative chemical vapor deposition under three different amounts of FeCl₃ used as oxidizing agents to form hybrid heterojunctions. Their microstructure, morphology, and electrical characteristics are studied. Particularly, current–voltage characteristics of the PPy/pc–ZnO heterojunctions are analyzed by defining an electrical equivalent circuit. The extracted parameters, together with the estimated heterojunction barrier height and the HOMO energy level of the PPy, indicate that a thermionic emission of holes at the heterojunction determines the saturation current of the diode at low voltage. For larger FeCl₃ amounts, the diode ideality factor increases indicating an increment of recombination by tunneling of charge carriers occurring at the heterojunction. This is attributed to a narrowing of the space charge region due to an increment of the number of charge carriers with a growing amount of FeCl₃. At high voltages, the PPy thickness influences the ohmic and space–charge limited current mechanisms at the bulk region. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1537–1544     

纳米石墨薄片/聚吡咯复合材料的制备及导电性能

膨胀石墨经过超声处理制备了纳米石墨薄片。以其为导电填料，对甲苯磺酸为掺杂剂，FeCl₃·6H₂O为氧化剂，引发吡咯单体发生原位聚合，制备出纳米石墨薄片/聚吡咯(NanoGs/PPy)复合材料。利用红外光谱(FTIR)、扫描电镜(SEM)和透射电镜(TEM)表征了材料的组成和结构。结果表明，石墨薄片被聚吡咯完全包覆；并且以纳米级尺寸分散在聚吡咯基体中。热失重(TG)分析和电导率测试结果表明，复合材料的耐热性能和导电性能较纯聚吡咯有所提高。     

Synthesis and characterization of poly (indene‐co‐pyrrole) nanofibers

Nanofibers of poly (indene‐co‐pyrrole) (CInPy) have been synthesized, using a facile chemical oxidative polymerization reaction. The effect of copolymerization was examined in view of the individually synthesized homopolymer nanostructures of polyindene (PIn) and polypyrrole (PPy). Morphological details of CInPy, studied using scanning electron microscopy (SEM) and transmission electron microscopy, (TEM) reveal the appearance of dense cottony mess, comprising of fine fibers with an average diameter of 5–10 nm. Chemical structural analysis of CInPy, conducted using ultraviolet‐visible (UV‐Vis), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR) spectroscopic techniques, reveals that both PIn and PPy are involved in the formation of copolymer organization. Fluorescence properties of nanosized copolymer are observed in the blue region, with emission λ_max placed at 395 nm. Conductivity of copolymer nanofibers (2.4 × 10^?3 S/cm) is consistent with the morphology and thermal stability properties of integral homo‐polymers. Improved thermal stability and processability along with the enhanced optical and electrical properties of copolymer nanostructures outfit it as a better promising material in optoelectronic and light emitting nanodevices, with reference to nanosized PIn and PPy. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and Properties of Polypyrrole/Chitosan Composite Hydrogels

Conducting polymer hydrogels consisting of polypyrrole (PPy) and chitosan (CS) are prepared by static polymerization of pyrrole using methyl orange (MO) as the dopant and Fe₂(SO₄)₃ as the oxidant in the CS aqueous solution. PPy/CS composite hydrogels not only have good electrical conductivities, but also exhibit excellent swelling/deswelling behaviors due to the participation of one-dimensional conducting PPy blocks in the hydrogel network. The effects of the amount of the oxidant and ionic strength on the physical properties of PPy/CS composite hydrogels are studied in detail. The results show that PPy/CS composite hydrogels have improved water absorbencies in saline solutions compared with the conventional polyelectrolyte hydrogel.     

Synthesis and characterization of conductive polypyrrole grown on the sulfonated surface of polyethylene films

Chemical synthesis of polypyrrole (PPy) was carried out in the presence of FeCl₃ aqueous solution. The grown PPy is fixed on the sulfonated surface of polyethylene (SPE) films, where the sulfonic groups act as counteranions to balance the positive charge of PPy, giving the composite material of PPy–SPE. For reasons of comparison, two types of polyethylene (PE) have been used, low and high densities with different degrees of sulfonation, SD (g/m²), defined as the ratio of weight increase to the area of the two surfaces of the sample. A series of reaction times was used to evaluate the variation of the electrical conductivity, σ (S/cm), of polypyrrole. It was found that σ increases as reaction time increases. To characterize the samples, Fourier transform infrared (FTIR) spectroscopy and conductivity measurements were performed.     

Facile Synthesis of Polyaniline‐Polypyrrole Nanofibers for Application in Chemical Deposition of Metal Nanoparticles

Polyaniline‐polypyrrole (PANI‐PPy) nanofibers with high aspect ratios have been synthesized by a one‐step, surfactant‐assisted chemical oxidative polymerization from mixtures of aniline (An) and pyrrole (Py) monomers. PANI‐PPy nanofibers synthesized with an excess of either PANI or PPy show similar spectral (UV‐vis and FT‐IR) characteristics as the individual homopolymers, whereas nanofibers from an equimolar mixture of An and Py display unique spectral characteristics. PANI‐PPy nanofibers undergo a spontaneous redox reaction with metal ions to produce metal nanoparticles with various morphologies and/or sizes. These findings may open new opportunities for synthesizing functional polymer nanofibers and metal nanoparticles with controllable sizes and/or morphologies.

     

Effect of CNT incorporation on PAN/PPy nanofibers synthesized by electrospinning method

In this study, carbon nanotubes (CNTs) added polyacrylonitrile/polypyrrole (PAN/PPy) electrospun nanofibers were produced. Average diameters of the nanofibers were measured as 268 and 153 nm for 10 and 25 wt% of PPy contents, respectively. A relatively higher strain to failure values (23.3%) were observed for the low PPy content. When as-grown CNTs (1 and 4 wt%) were added into the PAN/PPy blends, disordered nanofibers were observed to form within the microstructure. To improve the interfacial properties of CNTs/PAN/PPy composites, CNTs were functionalized with H₂SO₄/HNO₃/HCl solution. The functionalized CNTs were well dispersed within the nanofibers and aligned along the direction of nanofibers. Therefore, beads formation on nanofibers decreased. The impedance of the nanofibers was found to decrease with the PPy content and CNT addition. These nanofibers had a great potential to be used as an electrochemical actuator or a tissue engineering scaffold.     

In Situ Synthesis of Robust Conductive Cellulose/Polypyrrole Composite Aerogels and Their Potential Application in Nerve Regeneration

Nanostructured conductive polymers can offer analogous environments for extracellular matrix and induce cellular responses by electric stimulation, however, such materials often lack mechanical strength and tend to collapse under small stresses. We prepared electrically conductive nanoporous materials by coating nanoporous cellulose gels (NCG) with polypyrrole (PPy) nanoparticles, which were synthesized in situ from pyrrole monomers supplied as vapor. The resulting NCG/PPy composite hydrogels were converted to aerogels by drying with supercritical CO₂, giving a density of 0.41–0.53 g cm^?3, nitrogen adsorption surface areas of 264–303 m² g^?1, and high mechanical strength. The NCG/PPy composite hydrogels exhibited an electrical conductivity of up to 0.08 S cm^?1. In vitro studies showed that the incorporation of PPy into an NCG enhances the adhesion and proliferation of PC12 cells. Electrical stimulation demonstrated that PC12 cells attached and extended longer neurites when cultured on NCG/PPy composite gels with DBSA dopant. These materials are promising candidates for applications in nerve regeneration, carbon capture, catalyst supports, and many others.