Morphology control of chemically prepared polyaniline nanostructures: Effects of mass transfer

Chemical oxidative polymerization of aniline was carried out in a high viscosity reaction system, created by dissolving a high molecular weight, water-soluble polymer – polyethylene oxide – into the polymerization reaction. It was found that mass transfer, which likely influences the nucleation and growth of the polymerization products, has significant effects on the morphology of chemically prepared polyaniline (PANI) nanostructures. One-dimensional PANI nanostructures obtained in the high viscosity system had obviously smaller sizes and aspect ratios, as species diffusion was suppressed, especially with further increased system viscosity. The growth of PANI nanostructures appeared to be heavily diffusion-limited when aniline polymerization was carried out using a moderate oxidant or at very low monomer concentrations (e.g. 0.005 M) in the high viscosity system, resulting in “coral reef”-like PANI clusters. Promoting mass transfer for the polymerization carried out under very low monomer concentration in the high viscosity system was beneficial for preparation of uniform PANI nanofibers.     

Electrodeposited hybrid films of polyaniline and manganese oxide in nanofibrous structures for electrochemical supercapacitor

Hybrid films of polyaniline (PANI) and manganese oxide (MnO_x) were obtained through potentiodynamic deposition from solutions of aniline and MnSO₄ at pH 5.6. The hybrid films demonstrated characteristic redox behaviors of PANI in acidic aqueous solution. Characterization of the hybrid films by XRD indicated the amorphous nature of MnO_x in the films in which manganese existed in oxidation states of +2, +3 and +4, based on XPS measurement. Hybrid film of PANI and MnO_x, PM120 obtained from the solution of 0.1 M aniline and 120 mM Mn²⁺ displayed a well opened nanofibrous structure which showed an 44% increase in specific capacitance from that of PANI (408 F g^?1) to 588 F g^?1, measured at 1.0 mA cm^?2 in 1 M NaNO₃ (pH 1). The hybrid film kept more than 90% of its capacitance after 1000 charging-discharging cycles, with a coulombic efficiency of 98%. The specific capacitance of a symmetric capacitor using PM120 as the electrodes is 112 F g^?1.     

Polyaniline (PANI)–Co0.5Mn0.5Fe2O4 nanocomposite: Synthesis,characterization and magnetic properties evaluation

Polyaniline (PANI)/Cobalt-manganese ferrite, (PANI)/Co_0.5Mn_0.5Fe₂O₄, nanocomposite was synthesized by oxidative chemical polymerization of aniline in the presence of ammonium peroxydisulfate (APS). Microwave assisted synthesis method was used for the fabrication of core CoFe₂O₄ nanoparticles. The structural, morphological, thermal and magnetic properties of the nanocomposite were investigated in detail by X-ray diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). The average crystallite size of (PANI)/Co_0.5Mn_0.5Fe₂O₄ nanocomposite by the line profile method was 20±9 nm. The magnetization measurements revealed that (PANI)/Co_0.5Mn_0.5Fe₂O₄ nanocomposite has superparamagnetic behavior with blocking temperature higher than 300 K. The saturation magnetization of the composite is considerably low compared to that of CoFe₂O₄ nanoparticles due to the partial replacement of Co²⁺ ions and surface spin disorder. As temperature decreases, both coercivity and strength of antiferromagnetic interactions increase which results in unsaturated magnetization of the nanocomposite.     

An easy one-step electrosynthesis of graphene/polyaniline composites and electrochemical capacitor

An easy electrochemical technique is proposed to prepare electrochemically reduced graphene oxide (ERGO)/polyaniline (PANI) composites in a single step. The technique uses a two-electrode cell in which a separator soaked with an acid solution is sandwiched between graphene oxide (GO)/aniline films deposited on conductive substrates and an alternating voltage was applied to the electrodes. Successful preparations of ERGO/PANI composites were evidenced by characterizations due to UV–vis-NIR, FT-IR, XPS, XRD, and SEM measurements with free-standing films of ERGO/PANI obtained easily by disassembling the two-electrode cells. The ERGO/PANI films exhibited a high mechanical stability, flexibility, and conductivity (68 S cm⁻¹ for the composite film containing 80% ERGO) with nanostructured PANI particles (smaller than 20 nm) embedded homogeneously between the ERGO layers. The two-electrode cells acted as electrochemical capacitors (ECs) after a sufficient voltage cycling and exhibited relatively large specific capacitances (195–243 F g⁻¹ at a scan rate of 100 mV s⁻¹) with an excellent cycle life (retention of 83% capacitance after 20,000 charge–discharge cycles). Influences of the GO/aniline ratio, the sort of electrolytes, and the weight of the composite on the energy storage characteristics of ECs comprising the ERGO/PANI composites were also studied.     

Preparation and electrochemical investigation of the polyaniline/activated carbon nanocomposite for supercapacitor applications

The polyaniline (PANI)/activated carbon (AC) nanocomposite electrodes were prepared by electropolymerization of aniline monomers on the surface of AC/polyvinyl alcohol (PVA) electrodes for supercapacitor studies. Fourier transforms infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses were performed to characterize the structure and morphology of the nanocomposite electrodes. The electrochemical properties of the prepared nanocomposite electrodes and the supercapacitive behavior of the PANI, AC, and AC/PANI/PVA electrodes were investigated using cyclic voltammetry (CV) and galvanostatic charge/discharge measurements, respectively. Morphological studies showed that a thin film of PANI has been uniformly deposited on the porous surface of AC electrode, and an ordered arrangement of nanostructures with interlinked porous network has been made. Electrochemical measurements showed that AC particles prevent the degradation of PANI chains during charge/discharge cycles. The specific capacitance of the AC/PANI/PVA nanocomposite electrode was 338.15 F/g which is higher than that of the pristine AC electrode (0.08 F/g). This is due to the contribution of PANI chains by their pseudocapacitance (redox reaction) properties. Although the specific capacitance of PANI electrode (378.57 F/g) was greater than that of the nanocomposite electrode, the cyclic stability of the PANI electrode was lower than that of the AC/PANI/PVA nanocomposite electrode.     

Organosilane modified magnetite nanoparticles/poly(aniline-co-o/m-aminobenzenesulfonic acid) composites: Synthesis and characterization

A new strategy is employed for the preparation of hybrid nanocomposites based on silanized magnetite nanoparticles (MNPs-Si) and sulfonated polyanilines (SPAN). The method involves chemical oxidative copolymerization of orthoanilinic (OA) or metanilinic (MA) acid with aniline (ANI) in the presence of MNPs-Si. The nanocomposites, MNPs-Si/SPAN (OA/MA), were characterized for morphology and structural, thermal, electrical and magnetic properties. The composites have higher conductivities (0.25–0.39 S/cm) in comparison to pristine PANI (5.19 × 10⁻³ S/cm). The nanocomposites exhibit superparamagnetism.     

Characterization and AC conductivity of polyaniline–montmorillonite nanocomposites synthesized by mechanical/chemical reaction

Polyaniline–clay nanocomposites were prepared by solid state polymerization of aniline chloride in the interlayer of montmorillonite through the use of persulfate of ammonium as oxidant. The proportion of aniline to clay and the molar ratio of oxidant to aniline are being varied. The analyse of UV visible and FTIR spectroscopy demonstrated that aniline has been polymerized to polyaniline (PANI) in its conducting emeraldine form. The conformation adopted by PANI chains in the clay interlayer depended on the molar ratio of aniline to montmorillonite. Thermogravimetric analysis of the nanocomposites suggested that polyaniline chains are more thermally stable than those of free polyaniline prepared by solid–solid reaction. The AC conductivity data of different synthesized nanocomposites were analyzed as a function of frequency. Low frequency conductivities of polyaniline/montmorillonite nanocomposites materials ranges from 0.18 to 5.6 × 10^?3 S/cm. All characterization data were compared to those of free polyaniline that was synthesized using a solid–solid reaction.     

Application of kinetic,isotherm and thermodynamic models for the adsorption of Co(II) ions on polyaniline/polypyrrole copolymer nanofibers from aqueous solution

The aim of this research is to investigate sorption characteristics of polyaniline/polypyrrole copolymer nanofibers (PANI/PPy copolymer nanofibers) for the removal of Co(II) ions from aqueous solution. The adsorbent is characterized using FE-SEM, TEM, FTIR, TGA, DSC and BET surface area. The sorption of Co(II) ions by batch method is applied and the optimum conditions are investigated. In optimum condition, removal efficiency was 99.68% for 100 mg L⁻¹ Co(II) solution. It is found that temperature has a positive effect on the removal efficiency. It can be concluded that PANI/PPy copolymer nanofibers are potentially able to removal of Co(II) ions from aqueous solutions.     

Improved charging/discharging behavior of electropolymerized nanostructured composite films of polyaniline and electrochemically reduced graphene oxide

In this work, a simple electrochemical reduction procedure has been applied to nanostructured composite films of polyaniline (PANI) and graphene oxide (GO) having a globular surface morphology with the grain size of 50 nm. The reduction converts GO to reduced GO (rGO) which improves the electroactivity of the PANI composite films with 30%. Cyclic voltammetry confirmed the reduction of GO to rGO whereas electrochemical impedance spectroscopy showed that the rGO network increases the redox capacitance of the composite films with 15% to 77 mF cm⁻². In a three-electrode cell, the anodic charge of the PANI film containing GO increased with 18.7% during the potential cycling stability test for 10,000 cycles between −0.2 and 0.5 V, indicating that the film had a good stability against degradation. This composite film type still maintained a high capacitance of 15 mF cm⁻² in a symmetric two-electrode cell after 10,000 potential cycles between 0 and 0.4 V. The electrochemically prepared PANI composite films reported here are aimed to be used in capacitor applications where it is crucial to deposit thin PANI layers on well-defined small surfaces where other polymerization or deposition techniques cannot be used and in solid-state chemical sensors as ion-to-electron transducer interfaces.     

Simplifying the reaction system for the preparation of polyaniline nanofibers: Re-examination of template-free oxidative chemical polymerization of aniline in conventional low-pH acidic aqueous media

In this study, several polyaniline samples were prepared by oxidative chemical polymerization using only aniline, (NH₄)₂S₂O₈ and HCl in aqueous media at room temperature for morphological studies by SEM (scanning electron microscopy). The results show that polyaniline nanofibers can be obtained by template-free oxidative chemical polymerization in a conventional low-pH acidic aqueous medium (pH ～ 0) at room temperature. The study indicates that it is crucial to employ a mild post-polymerization processing procedure, such as dialysis, to preserve the as-formed morphology of polyaniline nanofibers. Our study also suggests that polyaniline could adopt the nanofiber structure as its intrinsic morphology when it is synthesized in a simple oxidative chemical polymerization system consisting of only aniline, (NH₄)₂S₂O₈ and HCl in an aqueous medium at room temperature.     

The role of polyaniline salts in the removal of direct blue 78 from aqueous solution: A kinetic study

Three polyaniline salts (PANI–H₂SO₄, PANI–H₃PO₄, and PANI–HNO₃) have been synthesized by chemical oxidative polymerization of aniline. They have been tested as adsorbents for the removal of the textile dye direct blue 78 (DB78) from aqueous solution. The interaction followed pseudo-second-order kinetics whether the rate of interaction was measured from the depletion of dye concentration in solution or the increase in the amount of dye adsorbed on the PANI surface. The removal rate was a function of the activity of the polymer as well as the reaction parameters of the polymer/dye system. The activity of the PANI depended on the polymerization conditions. These conditions involve the concentration of aniline, ammonium peroxydisulfate as oxidant, and sodium dodecylsulfate (SDS), the type of dopant acid (H₂SO₄, H₃PO₄, HNO₃), and the polymerization time. Higher removal rate was observed at oxidant/aniline mole ratio equals 1. The rate of removal was in the order PANI–H₃PO₄ > PANI–H₂SO₄ > PANI–HNO₃. The rate decreased with increasing the concentration of DB78 and pH. It increased with increasing the load of PANI. Pseudo-second-order kinetics, external surface adsorption, and intraparticle diffusion models were concurrently operating in the removal of DB78 with PANI.     

Covalently-grafted polyaniline on graphene oxide sheets for high performance electrochemical supercapacitors

A simple route to achieve covalently-grafted polyaniline (PANI)/graphene oxide (GO) nanocomposites has been developed. The synthesized composites showed a uniform hierarchical morphology of the PANI thin film and short rod-like nanostructures that had densely grown on the GO sheets, in contrast to the nonuniform morphology of noncovalently-grafted PANI/GO. Compared to pure PANI and noncovalently-grafted PANI/GO composites, the covalently-grafted PANI/GO composites possessed a much larger specific surface area and pore volume, which increased the accessible surface area for the redox reaction and allowed faster ion diffusion. This unique hierarchical morphology maximized the synergistic effect between PANI and GO, resulting in excellent electrochemical performance (capacitance 442 F/g of PANI/GO (6:1) vs. 226 F/g of pure PANI) and improved cycling stability (83% @ 2000 cycles of PANI/GO (6:1) vs. 54.3% @ 1000 cycles of pure PANI). The enhanced electrochemical performance demonstrates the advantage of the PANI/GO composites prepared via this covalent grafting method.     

Thermal conductivity of PVDF/PANI-nanofiber composite membrane aligned in an electric field

Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline(PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope(SEM) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction(XRD) and differential scanning calorimetry(DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from α-phase to β-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials.     

Kinetically controlled synthesis of carbon nanofibers with different morphologies by catalytic CO disproportionation over iron catalyst

Carbon nanofibers (CNFs) were synthesized by CO disproportionation on iron catalyst at CO concentration between 58.3% and 75.0%, H₂ concentration between 8.3% and 25.0% and reaction temperature between 833 and 913 K. The time-depending rate of CNFs growth as a function of time was determined by an on-line mass spectrometer and the morphologies of all CNFs products were observed by electronic microscopy. Not only the CNFs growth rate but also the morphology of the grown CNFs were shown to vary with the three operating variables. SEM and TEM images showed that the three-dimensional morphologies of the CNFs were twist, helical or straight and an interesting relationship between the maximal growth rate and the morphology was observed. When the growth rate was between 0.8 and 0.9 mmol/(s gcat), the CNFs were twist. As the growth rate increased to 1.0 mmol/(s gcat), more helical nanofibers appeared. Straight nanofibers were produced when the growth rate reached the level of 1.2 mmol/(s gcat). Finally when the rate of CNFs growth was high at 1.8 mmol/(s gcat), the absolute majority of the solid products was amorphous carbon coexisting with some short and thick nanofibers. Under different operating conditions, the crystal faces of the catalysts had different anisotropy properties for carbon deposition, thus producing CNFs with different morphologies.     

Three-dimensional hybrid materials of fish scale-like polyaniline nanosheet arrays on graphene oxide and carbon nanotube for high-performance ultracapacitors

Three-dimensional (3D) hybrid materials composed of 2D fish scale-like polyaniline (PANI) nanosheet arrays on graphene oxide sheets and carbon nanotubes were synthesized by a one-step process using a simplified template-free polymerization method. PANI nanosheet growth is proposed to be accomplished through electrostatic interaction, hydrogen bonding, and π–π stacking interaction. Such a material exhibits specific capacitances of 589 and 413 F g⁻¹ at 0.2 and 5 A g⁻¹, respectively, compared to pristine PANI of 397 and 180 F g⁻¹. After 1000 cycles, the composite still retains 81% of its initial capacitance, while PANI retains only 48%.     

Encapsulation of CoS nanoparticles in PAN electrospun nanofibers: Effective and reusable catalyst for ammonia borane hydrolysis and dyes photodegradation

In this study, the effective cobalt sulfide NPs were successfully encapsulated inside polyacrylonitrile (PAN) electrospun nanofibers. Typically, the solid NPs were in-situ synthesized by addition of ammonium sulfide drops to PAN/cobalt acetate solution. Electrospinning of the obtained colloid led to obtain good morphology polymeric nanofibers containing CoS NPs. Complete sheathing of the active nanoparticles did not affect their catalytic activity as the prepared mats revealed high performance toward hydrogen release from ammonia borane hydrolysis. Moreover, as a photocatalyst, a mat containing 2 wt% CoS could catalyze oxidation of methylene blue dye to be completely eliminated within 15 min. Furthermore, the introduced nanofibers photocatalytically enhanced complete degradation of the methyl red dye within relatively short time. The experimental results indicated that the optimum CoS content is 2 wt%, more increase in the concentration of the solid NPs leads to particles aggregation and consequently decrease the surface area. Beside the good activity obtained, the introduced immobilization strategy is considered an acceptable methodology to overcome the secondary pollution of the nanostructural photocatalysts because of the easy separation feasibility.     

The reduction of silver nitrate with various polyaniline salts to polyaniline–silver composites

A conducting polymer, emeraldine form of polyaniline (PANI), reduces silver nitrate to metallic silver. The composites of PANI and silver have been prepared at equimolar proportion of reactants. Seven acids, representing inorganic and organic acids, have been used to protonate PANI. The acids were selected with respect to their chemical indifference or the ability to precipitate or reduce silver(I) ions. The PANI–silver composites differed in the conductivity from 1.7 × 10^?6 S cm^?1 when PANI phosphate was used as a substrate to 22.8 S cm^?1 for PANI hydrochloride at comparable silver contents, 24 and 27 wt.%. The protonation state of PANI in PANI–silver composites was analyzed by FTIR spectroscopy. The composites contained spherical silver nanoparticles of 40–80 nm in size and also macroscopic particles, irrespective of PANI entering the reaction.     

The effect of graphite oxide on the thermoelectric properties of polyaniline

Graphite oxide (GO)/ordered polyaniline (PANI) composites have been prepared through an in situ polymerization. TEM, XRD, FTIR and XPS analyses show that the PANI grew along the surface of exfoliated GO as a template to form a more ordered structure with high crystallinity during polymerization. Compared with pure PANI, both higher electrical conductivity and higher Seebeck coefficient of GO/PANI composites result from the increased carrier mobility, which is confirmed by Hall measurement. Strong interactions exist between graphene oxide and PANI, including electrostatic forces, hydrogen bonding and π–π stacking. There is no significant difference in thermal conductivity between GO/PANI composites and PANI. The maximum electrical conductivity and Seebeck coefficient of the composites reach 751 S m^?1 and 28.31 μV K^?1, respectively. The maximum thermoelectric figure of merit is up to 4.86 × 10^?4, 2 orders of magnitude higher than that of pure PANI.     

One-step synthesis of electrically conductive polyaniline nanostructures by oxidative polymerization method

A simple, rapid and efficient route to prepare polyaniline nanostructures (PANI-NS) by “one-step chemical oxidative polymerization” method is described. This method possesses advantages in terms of good yield, short reaction time, neat conditions and cost-effectiveness. The morphology of the PANI-NS was investigated by field-emission scanning electron microscopy (FE-SEM). The average diameter of single PANI-NS was calculated to be ～376 nm. Results from UV–visible spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry (CV) reveals the existence of PANI units present in the polymeric nanostructures. Also, electrical conducting property of the PANI-NS was analyzed using four-probe measurement method.     

Effects of Al particle size and nitrogen pressure on AlN combustion synthesis

This study investigates the combustion synthesis of AlN fibers using an NH₄Cl additive and reports the effects of Al particle size (3, 30, and 180 µm) and N₂ pressure (0.10, 0.25, and 0.50 MPa) on the purity and morphology of AlN fibers. The combustion temperature was directly measured during the synthesis to elucidate the formation mechanism of the AlN fibers. The phase purity and morphology of the products were studied using X-ray diffraction and scanning electron microscopy, respectively. When the particle size of Al was reduced from 180 to 3 µm, the purity of the AlN product increased significantly owing to the large reaction area, which increased the combustion temperature. Furthermore, lower N₂ pressures enhanced the formation of AlN nanofibers due to the accelerated gasification of Al. The optimum values of the particle size of Al and the N₂ pressure for the formation of high-purity AlN nanofibers were found to be 3 µm and 0.10 MPa, respectively.