Introduction of methanol in the formation of polyaniline nanotubes in an acid-free aqueous solution through a self-curling process

This study reports the synthesis of polyaniline (PANI) nanotubes with the introduction of methanol in aqueous solutions. SEM images indicate that well-dispersed PANI nanotubes are produced when the concentration of methanol increases up to 1 M. On the other hand, polymers primarily form irregular agglomerates when only monomers and oxidant are used in the absence of methanol. Transmission electron microscopy (TEM) reveals that the resulting nanotubes have an outer diameter of about 200 nm and an inner diameter of 0-50 nm. Fourier transform infrared (FT-IR) spectra indicate that the intermediate samples obtained at a reaction time of around 60 min have a structure consisting of a head of phenazine-like units and a tail of para-linked aniline units. Ultraviolet-visible (UV-vis) spectra indicate that emeraldine salt polyaniline (ES-PANI) appears in sequence as the reaction time reaches 75 min. At the time interval of 60-75 min, the self-curling behavior of the PANI intermediates first appears at 60 min, and PANI nanotubes can be observed starting at 75 min. This is the first study to observe this self-curling process and propose that it explains the formation of PANI nanotubes. Noteworthily, the nanotubes transform into irregular agglomerates after a de-doping process.     

Polyaniline nanotubes: conditions of formation

The courses of aniline oxidation with ammonium peroxydisulfate in aqueous solutions of strong (sulfuric) and in weak (acetic) acids, followed by temperature and acidity changes, are different. In solutions of sulfuric acid, granular polyaniline (PANI) was produced; in solutions of acetic acid, PANI nanotubes were obtained. The external diameter of the nanotubes was 100–300 nm, the internal cavity 20–100 nm, and the length extended to several micrometres. The morphology of PANI, granular or tubular, depends on the acidity conditions during the reaction rather than on the chemical nature of the acid. PANI nanotubes were also produced when aniline was oxidized in the absence of any acid. The bulk conductivity of PANI prepared in solutions of acetic acid was 0.08–0.27 S cm^?1, depending on the acid concentration. Protonated PANI prepared in sulfuric and acetic acids were deprotonated with ammonium hydroxide to obtain PANI bases and the ammonium salt of the protonating acid. FTIR spectroscopy showed the differences in the molecular structure of the PANI bases. Irrespective of whether the polymerization was performed in solutions of sulfuric or acetic acid, PANI had hydrogen sulfate counter‐ions only. The PANI morphology is thus not controlled by the nature of counter‐ions. The acidity of the reaction medium determines the protonation of monomer, oligomer and polymer species. The chemistry of aniline oxidation is likely to be affected especially by the protonation of an intermediate in the pernigraniline form. It is proposed that, in the course of aniline oxidation, pH‐dependent self‐assembly of aniline oligomers predetermines the final PANI morphology. Copyright © 2005 Society of Chemical Industry     

Polyaniline synthesis catalysed by glucose oxidase

A novel method for synthesis of polyaniline (PANI) in aqueous media based on application of oxidizing-enzyme glucose oxidase (GOx) is reported. Hydrogen peroxide was produced during catalytic reaction of oxidizing-enzyme glucose oxidase from Penicillium vitale and initiated the polymerization of aniline. The increase in optical absorbance in the range of 340-700 nm was exploited for the monitoring of PANI polymerization process. The role of GOx in the formation of PANI, influence of the initial concentrations of GOx, and glucose and aniline monomer on the aniline polymerization rate was studied. The study of pH influence on polymerization rate showed that PANI polymerization was occurring in a broad pH range from the pH 2.0 to 9.0. Optimal polymerization/oligomerization temperature was found to be at 37 °C, which is also optimal for GOx-catalysed enzymatic reaction. After 10 days of continuous GOx-catalysed polymerization PANI appeared as colloid-microparticles visible by an optical microscope.     

Chemical and electrochemical synthesis of polyaniline/platinum composites

The synthesis of polyaniline/platinum composites (PANI/Pt) has been achieved using both chemical and electrochemical methods. The direct chemical synthesis of PANI/Pt proceeds through the oxidation of aniline by PtCl₆²⁻ in the absence of a secondary oxidant. SEM images of these samples indicate that the Pt particles are on the order of ∼1 μm for the chemically prepared composite. Electrochemical PANI/Pt synthesis is initiated by the uptake and reduction of PtCl₆²⁻ into an a priori electrochemically deposited PANI film. This method produces a uniform dispersion of Pt particles with smaller particles with diameters ranging between 200 nm and 1 μm. The results indicate that electrochemical methods may be more suitable for controlling particle dimension. Both materials show reduced proton doping relative to PANI without Pt, indicating the metal particles directly influence proton doping and the oxidation state of the polymer. The electrochemical data indicate that the conductivity in solution is sufficient such that the normal acid doping is attainable for PANI/Pt produced using either synthetic method.     

Polyaniline prepared in solutions of phosphoric acid: Powders, thin films, and colloidal dispersions

Polyaniline (PANI) has been prepared by the oxidation of aniline with ammonium peroxydisulfate in the 0-4 M phosphoric acid. The maximum conductivity of PANI, 15.5 S cm⁻¹, was found with PANI prepared in the presence of 1 M phosphoric acid. The mass loss after deprotonation with ammonium hydroxide revealed that relatively large amounts of phosphoric acid were associated with PANI if the polymerization had been carried out at higher acid concentration. This suggests the protonation of both the imine and amine nitrogens in PANI, the increased adsorption of phosphoric acid by PANI, or the presence of polyphosphate counter-ions. The increasing content of phosphoric acid is also reflected in the increase of sample density. FTIR spectra of ammonium salts collected after deprotonation proved that the counter-ions of the sulfate type, resulting from the decomposition of peroxydisulfate, always participated in the protonation of PANI. The proportion of sulfate to phosphate counter-ions was reduced as the concentration of phosphoric acid in the medium increased.Thin PANI films were produced in situ on glass surfaces immersed in the reaction mixture during the polymerization of aniline. Optical absorption has been used to assess their thickness, 70-140 nm, which was found to be virtually independent of the acid concentration. The film conductivity was comparable with the conductivity of the PANI powders produced at the same time. Colloidal dispersions were obtained when the reaction mixture contained poly(N-vinylpyrrolidone). The particle size, 200-260 nm, and polydispersity, determined by dynamic light scattering, were virtually independent of the concentration of phosphoric acid. The films produced on glass during the dispersion polymerization of aniline were thinner, 20-90 nm, compared with those grown in the precipitation polymerization.     

Ultrafine nano-colloid of polyaniline

We report a synthesis of polyaniline (PANI) suspension of particles with size of about 2-3 nm. This nano-colloid was obtained by aniline oxidative polymerization in dilute and semi-dilute solutions of sodium poly(styrene sulfonate) (PSSNa) with molecular weight equal to 6800 g/mol or higher. The ionic strength of the solution was about 1×10⁻² mol/l, which corresponds to aniline (and, respectively, PANI) concentration lower than 4.6×10⁻² mol/l in 5 M solution of formic acid. To the best of our knowledge, it is the first communication dealing with preparation of particles with a molecular scale dimensions, using a rigid backbone polymer with a very strong intermolecular interactions. Important modification of the electronic properties of such dispersed PANI, compared to those of the well-known bulk PANI, was observed.     

Chemical anchoring of silica nanoparticles onto polyaniline chains via electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of SiO2

Chemical anchoring of silica nanoparticles onto polyaniline (PANI) chains was conducted through electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of silica nanoparticles. The grafting of N-substituted aniline on surfaces of silica nanoparticles were realized through hydrolysis of triethoxysilylmethyl N-substituted aniline (ND42) and the following condensation reaction with silanol groups on surfaces of SiO₂. Organic-inorganic interactions between PANI and SiO₂ involved in electro-co-polymerization process pushed the polymer chains apart and so facilitated the 1D growth of the polymer. Hence, the obtained hybrid film PANI/ND42-SiO₂ displayed nano-fibrous morphologies (ca. 50 nm in diameter). Consequently, PANI/ND42-SiO₂ exhibited an average specific capacitance of 380 F g⁻¹, ca. 40% higher than that of PANI/SiO₂ (276 F g⁻¹). The hybrid film also showed improved cyclic stability.     

Multi-wall carbon nanotubes coated with polyaniline

Multi-wall carbon nanotubes (CNT) were coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. The content of CNT in the samples was 0-80 wt%. Uniform coating of CNT with PANI was observed with both scanning and transmission electron microscopy. An improvement in the thermal stability of the PANI in the composites was found by thermogravimetric analysis. FTIR and Raman spectra illustrate the presence of PANI in the composites; no interaction between PANI and CNT could be proved. The conductivity of PANI-coated CNT has been compared with the conductivity of the corresponding mixtures of PANI and CNT. At high CNT contents, it is not important if the PANI coating is protonated or not; the conductivity is similar in both cases, and it is determined by the CNT. Polyaniline reduces the contact resistance between the individual nanotubes. A maximum conductivity of 25.4 S cm⁻¹ has been found with PANI-coated CNT containing 70 wt% CNT. The wettability measurements show that CNT coated with protonated PANI are hydrophilic, the water contact angle being ∼40°, even at 60 wt% CNT in the composite. The specific surface area, determined by nitrogen adsorption, ranges from 20 m² g⁻¹ for protonated PANI to 56 m² g⁻¹ for neat CNT. The pore sizes and volumes have been determined by mercury porosimetry. The density measurements indicate that the compressed PANI-coated CNT are more compact compared with compressed mixtures of PANI and CNT. The relaxation and the growth of dimensions of the samples after the release of compression have been noted.     

Preparation of PANI-coated poly(styrene-co-styrene sulfonate) nanoparticles

Poly(styrene-co-styrene sulfonate) (PS-PSS) latexes have been coated with thin overlayer of polyaniline (PANI) to produce electrically conductive ‘core-shell’ particles (PANI/PS-PSS) in the size of range 30-50 nm in diameter. PS-PSS core particles were prepared by radical emulsion copolymerization and PANI was oxidatively polymerized using ammonium peroxydisulfate (APS) on the surface of PS-PSS latex. PANI thin overlayer was observed in transmission electron microscopy (TEM) images indicating polymerization of aniline takes place preferably on the PS-PSS surface rather than in the aqueous bulk phase. Elemental analysis revealed that the weight percent of styrene sulfonate in PS-PSS copolymer was ca. 5.4% and the conductivities of PANI/PS-PSS pellets were greatly increased with the increase of nitrogen content. Thermal gravimetric analysis (TGA) thermograms showed two main degradation stages beginning at 360 and 460°C that correspond to the decomposition of PS-PSS and PANI, respectively.     

In-Situ Infrared Study of the Synthesis of Polyaniline Under Acid and Neutral pH

In-situ infrared study of polyaniline (PANI) synthesis showed that the reaction initiated at pH = 1.5 produced a granule PANI microstructure via para-linked dimers of 4-aminodiphenylamine, exhibiting γ(C–H) at 802 cm^?1; the reaction initiated at pH = 5.0 and 7.0 produce fiberous, and planar microstructures via ortho-linked dimers of 1,2-aminodiphenylamine and phenazine, exhibiting γ(C–H) at 738 and ν(C=N) at 1446 cm^?1. The doped PANI that was produced at pH less than 5.0 showed a feature-less IR background absorption above 1600 cm^?1. This absorption could correspond to π-electron delocalization as an indicative of polyaniline conductivity.     

The reaction of polyaniline with iodine

Polyaniline (PANI) (emeraldine) base has been exposed to iodine in an ethanol-water suspension. The conductivity of PANI increased from 10⁻⁹ S cm⁻¹ to 10⁻⁴ S cm⁻¹ already at the molar ratio [I₂]/[PANI] = 1, and a higher content of iodine had only a marginal effect. This is the result of the protonation of PANI base with hydriodic acid, which is a by-product of the oxidation of the emeraldine form of PANI to pernigraniline constitutional units. The reaction is discussed on the basis of FTIR spectra. An alternative reaction, a ring-iodination of PANI, is marginal. Only one iodine atom substitutes a hydrogen atom in about 12 aniline units, even at high iodine concentration, [I₂]/[PANI] = 8. The film of polyaniline base can be used in sensing iodine; after exposure to the iodine vapor, the conductivity of the polyaniline film increased.     

The mechanism of the oxidative polymerization of aniline and the formation of supramolecular polyaniline structures

Polyaniline is one of the most important conducting and responsive polymers. A molecular mechanism for the oxidation of aniline is proposed. This mechanism explains the specific features of aniline oligomerization and polymerization in various acidity ranges. The formation of polyaniline precipitates, colloids and thin films is reviewed and discussed on the basis of the chemistry of aniline oxidation. The generation of nanostructures, i.e. granules, nanotubes, nanowires and microspheres, is also considered. Oligomers containing phenazine constitutional units play an important role in self‐assembly to form templates. Polyaniline chains then grow from these templates and produce the various individual morphologies. Copyright © 2008 Society of Chemical Industry     

Polyaniline-intercalated graphene oxide sheet and its transition to a nanotube through a self-curling process

This study reports the preparation of graphene oxide (GO)/polyaniline (PANI) nanotubes through polymerizing aniline monomers in the presence of GO sheets. Transmission electron microscopy (TEM) reveals that the obtained GO/PANI nanotubes have an outer diameter of ～120 nm and an inner diameter of 15 nm. Fourier transform infrared (FT-IR) spectra and thermogravimetric analysis (TGA) curves verify the coexistence of GO and PANI in the produced nanotubes. X-ray diffraction patterns identify the intercalation of PANI chains between GO sheets. Specifically, SEM images reveal the formation of polyaniline-intercalated GO sheets in earlier stage. Subsequently, these initially-formed GO/PANI sheets would transform into nanotubes through a self-curling process. The changes of molecular structures and doping states of polyaniline molecules during the polymerization process are thought to be responsible for the self-curling behavior. Compared with the pristine PANI nanotubes, the GO/PANI nanotubes exhibit an even higher electrical conductivity and manifest their great potential in applications of various electrochemical devices.     

The oxidation of aniline with silver nitrate to polyaniline-silver composites

Silver nitrate oxidizes aniline in the solutions of nitric acid to conducting nanofibrillar polyaniline. Nanofibres of 10-20 nm thickness are assembled to brushes. Nanotubes, having cavities of various diameters, and nanorods have also been present in the oxidation products, as well as other morphologies. Metallic silver is obtained as nanoparticles of ∼50 nm size accompanying macroscopic silver flakes. The reaction in 0.4 M nitric acid is slow and takes several weeks to reach 10-15% yield. It is faster in 1 M nitric acid; a high yield, 89% of theory, has been found after two weeks oxidation of 0.8 M aniline. The emeraldine structure of polyaniline has been confirmed by FTIR and UV-vis spectra. The resulting polyaniline-silver composites contain 50-80 wt.% of silver, close to the theoretical expectation of 68.9 wt.% of silver. The highest conductivity was 2250 S cm⁻¹. The yield of a composite is lower when the reaction is carried out in dark, the effect of daylight being less pronounced at higher concentrations of reactants.     

The electrochemical copolymerization of aniline with 2,4-diaminophenol and the electric properties of the resulting copolymer

The copolymerization of aniline and 2,4-diaminophenol (DAP) was first carried out in an acidic solution under a constant potential of 0.75 V. The copolymerization rate was found to increase with an increasing ratio of monomer DAP to aniline in the mixture. The opposite is true of the electrochemical copolymerization of aniline and o-aminophenol or m-aminophenol. The difference is due to the two kinds of electron-donating groups in DPA. Poly(aniline-co-2,4-diaminophenol) (PADAP), when synthesized under optimal conditions, has a good redox activity from pH < 1 to 11.0 in a wide potential region. Its conductivity is 0.26 S cm⁻¹, which is very close to that of polyaniline synthesized under the same conditions in the absence of DAP. The pH dependence of PADAP conductivity was found to be better than that of polyaniline. PADAP that is synthesized under optimal conditions has unique magnetic resonance properties in NMR and ESR; molecules that are synthesized in the presence of other DAP to aniline concentration ratios have different properties. The monomer concentration ratio in the mixture and the applied potential strongly affect the properties of PADAP.     

Polyaniline-carbon composite films as supports of Pt and PtRu particles for methanol electrooxidation

Vulcan XC-72 carbon black particles (average size: ca. 50 nm) was incorporated into polyaniline (PANI) matrix by an electrochemical codeposition technique during the electropolymerization process. The doping by carbon particles leads to a higher polymeric degree and a lower defect density in the PANI structure. Furthermore, the incorporation of carbon particles not only increases the electrochemical accessible surface areas (S_a) and electron conductivity of the PANI film, but also decreases charge transfer resistance at PANI/electrolyte interfaces. Therefore, as expected, a fabricated PANI + C composite film with dispersed Pt and PtRu particles exhibited excellent electrocatalytic activity for methanol oxidation due to better Pt dispersion and utilization. The PANI + C composite film is more promising as a support material in electrocatalysis than a PANI film. Meanwhile, a new application for regular carbon black as a doping material into conducting polymer for electrocatalysis was thus demonstrated.     

Facile synthesis and morphology control of graphene oxide/polyaniline nanocomposites via in-situ polymerization process

This study reports the synthesis of graphene oxide (GO)/polyaniline (PANI) nanocomposites with controllable morphologies through in-situ polymerization of aniline monomers in the presence of GO sheets. Specific reaction parameters including solution acidity, aniline concentration, and reaction temperature are used to control the final shape of the composite product. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images are used to explore the morphology of the composite. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), FT–IR and UV–vis spectrophotometers are utilized to characterize the intermediates and the final products of the GO/PANI composites. Experiment results reveal that the polymerization operated in low acidity and low temperature conditions inclines to form GO/PANI nanotubes. On the other hand, the polymerization operated in high acidity inclines to form either nanospheres or aligned nanofiber arrays. These different morphologies are resulted from different polymerization routes and the formation mechanisms of these different shapes of nanocomposites are explored. Among the various nanocomposites, the GO/PANI nanospheres exhibit a highest electrochemical surface area. This study provides a facile and effective strategy to control the morphology of GO/PANI nanocomposites with characteristic electrochemical property.     

Electrochemical polymerization and initial corrosion properties of polyaniline-benzoate film on aluminum

Electrochemical synthesis of polyaniline (PANI) on aluminum electrode from aqueous solution of 0.25 mol dm⁻³ aniline and 0.2 mol dm⁻³ sodium benzoate has been investigated under potentiodynamic and galvanostatic conditions. Initial corrosion behavior of aluminum and PANI coated aluminum electrode exposed to 3% NaCl has been investigated using electrochemical potentiodynamic and impedance spectroscopy technique (EIS). It was shown that PANI coating initially provide corrosion protection of aluminum, decreasing the corrosion current density at least 15 times.     

Polyaniline/multi-walled carbon nanotube composites with core-shell structures as supercapacitor electrode materials

Composites with core-shell structures consisting of polyaniline and carbon nanotubes were prepared via in situ polymerization of aniline monomers by using multi-walled carbon nanotubes with minimized defects as templates. The strong interaction in such conjugated systems greatly improves the charge-transfer reaction between polyaniline and the carbon nanotube. Influences of the thickness of the polyaniline layer on the surface of the carbon nanotubes on the electrochemical properties of the resulting composites are discussed. The highest specific capacitance of 560 F/g was achieved by using a composite with 66 wt% polyaniline content as the supercapacitor electrode. Additionally, enhancement of the capacity retention was observed, with the composite losing only 29.1% of the maximum capacity after 700 cycles, and then remaining stable.     

Electrosynthesis of Polyaniline/SiO2 Composite at high pH in the Absence of Extra Supporting Electrolyte

Summary Electropolymerization of aniline was investigated in solutions of different pH from 1.0 to 12.1 without extra supporting electrolyte. FT-IR Spectra of the polymers display characteristic absorptions for polyaniline (PANI) including that for protonated PANI, although some of the polymers were obtained in solutions of high pH. PANI obtained from acidic solutions displayed the usual electroactivities in 0.5 mol·l^-1 H₂SO₄, while those obtained from solutions of pH 6.0 to 12.1 showed an unusual redox pair additionally on cyclic voltammograms at 0.04 V vs. SCE. This redox pair can be ascribed to the redox of phenazine ring, originated from the attack of nitrenium cation to PANI chain in the ortho-position. Electrocodeposition of PANI and SiO₂ was conducted through electrophoresis of silica particles towards anode as aniline anodically electropolymerized. Energy dispersive X-ray diffraction (EDX) analysis and SEM inspection were performed on obtained PANI/SiO₂ to investigate the composite film.