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.     

Hybrid composites of conductive polyaniline and nanocrystalline titanium oxide prepared via self-assembling and graft polymerization

After TiO₂ nanoparticles were surface modified, conductive polyaniline (PANI) layer was chemically grafted on the surface of the self-assembled monolayer (SAM) coated TiO₂ nanoparticles, resulting in PANI/SAM-TiO₂ composites. In the preparation process of the hybrid composites, γ-aminopropyltriethoxysilane was used as a coupling agent to form a dense aminopropylsilane monolayer with active sites for the graft polymerization of aniline. The resulted composite nanoparticles were characterized by using TEM, FTIR, TGA, and UV-vis-diffuse reflectance spectroscopy. The thermogravimetric analysis confirmed that the inserted SAM layer improved the thermal stability of the PANI-TiO₂ nanocomposites. Compared with neat-TiO₂ nanoparticles without any surface modification, moreover, the PANI/SAM-TiO₂ nanocomposites showed better photocatalytic activity in photodegradation of methyl orange under sunlight, which was partly attributed to the sensitizing effect of PANI.     

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.     

High capacitance properties of polyaniline by electrochemical deposition on a porous carbon substrate

Electrochemical deposition of polyaniline (PANI) is carried out on a porous carbon substrate for supercapacitor studies. The effect of substrate is studied by comparing the results obtained using platinum, stainless steel and porous carbon substrates. PANI deposited at 100 mV s⁻¹ sweep rate by potentiodynamic technique on porous carbon substrate is found to possess superior capacitance properties. Experimental variables, namely, concentrations of aniline monomer and H₂SO₄ supporting electrolyte are varied and arrived at the optimum concentrations to obtain a maximum capacitance of PANI. Low concentrations of both aniline and H₂SO₄, which produce PANI at low rates, are desirable. The PANI deposits prepared under these conditions possess network morphology of nanofibrils. Capacitance values as high as 1600 F g⁻¹ are obtained and PANI coated carbon electrodes facilitate charge-discharge current densities as high as 45 mA cm⁻² (19.8 A g⁻¹). Electrodes are found to be fairly stable over a long cycle-life, although there is some capacitance loss during the initial stages of cycling.     

Insight into the improvement of rate capability and cyclability in LiFePO4/polyaniline composite cathode

A simple and efficient strategy was employed to enhance high-rate performance for carbon-coated LiFePO₄ (C-LFP) by incorporating with conducting polymer polyaniline (PANI). C-LFP was synthesized via a solid state reaction whereas PANI was formed in situ by chemical oxidative polymerization of aniline with ammonium persulfate as an oxidizer to achieve the C-LFP/PANI composites. Specific capacities as high as 165 mAh g⁻¹ at 0.2 C, 133 mAh g⁻¹ at 7 C and 123 mAh g⁻¹ at 10 C were obtained in C-LFP/7 wt.% PANI composite. Moreover, the composite exhibits remarkably improved cyclability as compared with the parent C-LFP. The mechanism has been carefully investigated for the improvement in the electrochemical performance. Experimental results show that the charge transfer impedance decreases significantly and the cathode surface becomes much smooth over cycling with modification of conductive PANI. The incorporated PANI can work not only as an additional host for Li⁺-ion insertion/extraction, but also as a binder to modify the electrode surface and a container for electrolyte to penetrate into C-LFP particles.     

The influence of decanethiol/4-aminothiophenol mixed monolayers on the electrodeposition of polyaniline thin films

Polyaniline thin films were electrodeposited onto naked Au and thiol-modified Au electrodes by potential cycling. Self-assembled monolayers (SAMs) contained 4-aminothiophenol (4-ATP) and n-decanethiol (DT) in varying molar ratios. The electropolymerization of aniline at these surfaces is strongly influenced by the composition of the monolayer. When the potential was cycled between 0 and 0.8 V, the polymerization of aniline initiated at 4-ATP sites in the SAMs. The electrical conductivity of the films was found to increase as the mole fraction of 4-ATP in the SAM increased. When the potential was cycled between 0 and 1.0 V, polymerization of aniline is initiated both at the surface and by the direct oxidation of aniline monomers in solution. Nevertheless, the composition of the SAM has a profound influence on the properties of the polyaniline films, especially the electrical conductivity, which increases with 4-ATP mole fraction up to a value of 0.77, and then decreases dramatically. The amount of 4-ATP in the SAM influences the rate of aniline oxidation, which determines the overall polymerization rate, and, in turn, influences the thin film conductivities. When the rate of monomer oxidation is too high, the films are over oxidized and lose conductivity. On the other hand, when the monomer oxidation rate is too low, the oligomer number suffers, and the conductivity drops. Thus, with respect to the electrical conductivity, there appears to be an optimum rate of aniline oxidation, which can be controlled by use of the appropriate SAM.     

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF₄/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.     

Electropolymerization of aniline in acid media on the bare and chemically pre-treated aluminum electrodes: A comparative characterization of the polyaniline deposited electrodes

The electrosynthesis of polyaniline on the bare aluminum and pre-treated aluminum surface achieved in aqueous H₂PtCl₆ solution saturated with NaF for few seconds is described. The effect of some factors such as pre-treatment time, aniline and sulfuric acid concentrations on the electropolymerization process was investigated and optimum conditions were obtained. The stability of polyaniline film on the pre-treated aluminum electrode (Al-Pt) was studied as function of the potential imposed on the electrode. For applied electrode potentials of 0.1-0.7 V, the first-order degradation rate constant, k, of polyaniline film varies between 1 × 10⁻⁶ and 2 × 10⁻⁵ s⁻¹, and a relatively low slope (i.e. 2.1) was obtained for the plot of log k versus E. The coatings were characterized by scanning electron microscopy (SEM), and cyclic voltammetric behavior of the polyaniline-deposited Al electrode (Al/PANI) and polyaniline-deposited Al-Pt electrode (Al-Pt/PANI) in 0.1 H₂SO₄ solutions is described. The electrocatalytic activity of the Al-Pt/PANI electrode against para-benzoquinone/hydroquinone (Q/H₂Q) and Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox systems was investigated and the obtained results are compared with those obtained on Al/PANI and bulk Pt electrodes.     

Insights into the surface and redox properties of single-walled carbon nanotube—cobalt(II) tetra-aminophthalocyanine self-assembled on gold electrode

This paper describes for the first time the electrochemical properties of redox-active self-assembled films of single-walled carbon nanotubes (SWCNTs) coordinated to cobalt(II)tetra-aminophthalocyanine (CoTAPc) by sequential self-assembly onto a preformed aminoethanethiol (AET) self-assembled monolayer (SAM) on a gold electrode. Both redox-active SAMs (Au-AET-SWCNT and Au-AET-SWCNT-CoTAPc) exhibited reversible electrochemistry in aqueous (phosphate buffer) solution. X-ray photoelectron spectroscopy (XPS) confirmed the appearance on the gold surface of the various elements found on the SAMs. Atomic force microscopy (AFM) images prove, corroborating the estimated electrochemical surface concentrations, that these SAMs lie normal to the gold surface. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)₆]^3−/4− as a redox probe revealed that the Au-AET-SWCNT-CoTAPc showed much lower (∼10 times) electron-transfer resistance (R_et) and much higher (∼10 times) apparent electron-transfer rate constant (k_app) compared to the Au-AET-SWCNT SAM. Interestingly, a preliminary electrocatalytic investigation showed that both SAMs exhibit comparable electrocatalytic responses towards the detection of dopamine in pH 7.4 phosphate buffer solutions (PBS). The electrochemical studies (cyclic voltammetry (CV) and EIS) prove that SWCNT greatly improves the electronic communication between CoTAPc and the Au electrode surface.     

Electrochemical nitrite nanosensor developed with amine- and sulphate-functionalised polystyrene latex beads self-assembled on polyaniline

Aniline doped with polyvinyl sulphonate (PV-SO₃⁻) was electropolymerised on screen printed carbon (SPCE) and glassy carbon (GCE) electrodes. Then nano-structured polystyrene (PS_NP) latex beads functionalised with amine (PS_NP-NH₂) and sulphate (PS_NP-OSO₃⁻) were self-assembled on the modified SPCE and GCE. The resultant polyaniline nanocomposites (PANI|PS_NP-NH₂ or PANI|PS_NP-OSO₃⁻) were characterised by cyclic voltammetry (CV), UV-vis spectroscopy and scanning electron microscopy (SEM). Brown-Anson analysis of the multi-scan rate CV responses of the various PANI films gave surface concentrations of the order of 10⁻⁸ mol cm⁻². UV-vis spectra of the PANI films dissolved in dimethyl sulphoxide showed typical strong absorbance maxima at 480 and 740 nm associated with benzenoid π-π* transition and quinoid excitons of polyaniline, respectively. The SEM images of the PANI nanocomposite films showed cauliflower-like structures that are <100 nm in diameter. When applied as electrochemical nitrite sensor, sensitivity values of 60, 40 and 30 μA/mM were obtained for electrode systems containing PANI|PS_NP-NH₂, PANI and PANI|PS_NP-SO₃⁻, respectively. The corresponding limits of detection of the sensors were 7.4, 9.2 and 38.2 μM NO₂⁻.     

Electrocatalytic reduction of bromate ion using a polyaniline-modified electrode: An efficient and green technology for the removal of BrO3 in aqueous solutions

The electrocatalytic reduction of bromate ion (BrO₃⁻) was investigated in a three-electrode system using polyaniline (PANI) as the electrode material. Bromate ion reduction and Br⁻ removal were observed during electrochemical treatment because of the catalytic and doping capabilities of the PANI film. BrO₃⁻ removal efficiency in the 0.10 mol L⁻¹ Na₂SO₄ supporting electrolyte achieved 99% at pH 7 in 25 min, with no bromide ion detected in the solution. Optimal removal was found in pH range 6-7, and the pH of the solution had a significant impact on bromate reduction. A reduction mechanism was also discussed by analyzing the cyclic voltammograms of the reduction process and X-ray photoelectron spectra of the main elements (N 1s and Br 3d) on the PANI surface. We propose that during the electrocatalytic reduction process, bromate is reduced to bromide because of the loss of electrons from the nitrogen atoms on the PANI chains. The doping of the resultant Br⁻ ions in the PANI film has an important role in avoiding further oxidation of Br⁻ to BrO₃⁻. The used PANI film can be regenerated by de-doping the Br⁻ ions with a 0.5 mol L⁻¹ H₂SO₄ solution. Thus the process can be considered efficient and green.     

Facile synthesis of SBA-15/polyaniline nanocomposites with high electrochemical activity under neutral and acidic conditions

A facile synthesis of SBA-15/polyaniline (PANI) nanocomposites was developed via chemical polymerization in a pH 3 solution based on the electrostatic adsorption of positively charged anilinium ions on negatively charged SBA-15. X-ray diffraction, N₂ sorption isotherms, transmission electron microscopy and scanning electron microscopy characteristics indicated that PANI chains were distributed both on the inside and outside surfaces of the SBA-15 pores. A possible synthetic scheme for the creation of nanocomposites has been proposed. The SBA-15/PANI nanocomposites showed high, stable electrochemical activity in neutral and acidic conditions. The preliminary use of the SBA-15/PANI nanocomposites as an electroactive support for the selective detection of uric acid (UA) in the presence of a large excess of ascorbic acid (AA) demonstrates this material’s potential for use in electrochemical biosensors.     

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.     

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.     

Electrochemical synthesis of WO3/PANI composite for electrocatalytic reduction of iodate

Composite film of polyaniline (PANI) and tungsten oxide (WO₃) was electrodeposited by cyclic voltammetric technique from a solution of aniline and tungstic acid. The obtained WO₃/PANI film displayed a significant enhancement of electrocatalytic activity for iodate reduction and a better stability than that of pure WO₃ and PANI films. Result of amperometric experiment revealed a good linear relationship with concentration of IO₃⁻ from 20 to 500 μM, with a high sensitivity of 0.54 μA/μM and a detection limit of 2.7 μM for the determination of iodate. This composite film was also successfully applied in determination of iodate in commercial table salt.     

Ion transport through a porphyrin-terminated hybrid bilayer membrane

A hybrid bilayer membrane (HBM) has been prepared on a glassy carbon electrode (GCE). The HBM consists of an inner layer of n-hexadecylamine (HDA) covalently attached at the GCE and an out-layer of tetra-(N-hexadecylpyridiniurnyl)porphyrin (TC₁₆PyP). The HDA was covalently bounded on the carbon surfaces through its primary amine under cyclic voltammetric potential scans forming a self-assembled monolayer (SAM). The TC₁₆PyP forms a second layer on top of the HDA layer due to hydrophobic interaction. The TC₁₆PyP/HDA/GCE assembly has been utilized to study ion transport through hybrid bilayer membranes. The ion transport through this porphyrin-terminated HBM has been found to strongly dependent on pH. It allows negatively charged redox ions, Fe(CN)₆³⁻, to penetrate at pH <6 while repelling positively charged Ru(NH₃)₆³⁺. However, no faradaic current has been detected at pH >6 with either ions. We believe that electrostatic interaction between the redox ions and the charged membrane is the main reason for this pH dependent ion transport.     

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.     

Fabrication of honeycomb-patterned polyaniline composite films using chemically modified polyaniline nanoparticles

A novel polyaniline composite was prepared by in situ ring-opening polymerization of ε-caprolactone in the presence of chemically modified polyaniline nanoparticles (PANI-NPs) using Sn(Oct)₂ as an initiator, which exhibited a high solubility in organic solvent to enable the fabrication of stable honeycomb-patterned thin films by casting the PANI composite solutions under humid conditions. The chemically modified PANI-NPs were produced from the polymerization of aniline in the cationic surfactant of cetyl trimethyl ammonium bromide (CTAB). The polyaniline composites were characterized via Fourier transform infrared, ultraviolet–visible spectroscopy, X-ray diffraction, transmission electron microscopy, and thermogravimetry. The analyses indicated that the PANI-NPs were well incorporated in the poly(ε-caprolactone) (PCL) backbone. The patterned PANI composite films showed high DC conductivity up to 10⁻² S/cm, which can be useful in applications such as bio-sensing, bio-nanotechnology, biological science, and medicine.     

The electrochemical reduction of PdCl4 and PdCl6 in polyaniline: Influence of Pd deposit morphology on methanol oxidation in alkaline solution

The controlled uptake and electrochemical reduction of metal precursors PdCl₄²⁻ and PdCl₆²⁻ in polyaniline (PANI) is demonstrated. The formation of PANI/Pd composites is achieved with a reduction in proton doping and an increase in the oxidation of the polymer with Pd deposits physically blocking the nitrogen groups. High surface area filaments (PdCl₄²⁻) or a rough encapsulation (PdCl₆²⁻) of Pd metal on PANI are obtained. The structural differences highlight the influence of the metal precursor oxidation state on the morphology of the Pd deposits in PANI. Thermal gravimetric analysis provides an estimate of the Pd content for each composite of ∼40%. X-ray Photoelectron Spectroscopy and X-ray-excited Auger Electron Spectroscopy analyses confirm the deposition of Pd metal. The catalytic oxidation of methanol was demonstrated for both PANI/Pd composites in alkaline solutions that prohibit proton doping of the polymer. The data indicates that Pd metal acts as a solid-state dopant that may delocalize the charge on the polymer backbone to maintain conductivity. Methanol oxidation at PANI/Pd composites produced using PdCl₄²⁻ was enhanced relative to the composite produced using PdCl₆²⁻ and a planar Pd electrode. Comparison of PANI/Pd composite produced using PdCl₄²⁻ with other Pd catalysts from the literature indicates surface poisoning is reduced when Pd is coupled with the polymer. The composite is robust and stable in alkaline solution with the charge density decreasing by 5% on the positive scan and 13% on the negative scan after 200 voltammetric cycles. The data also indicates that the reductive desorption of surface contaminants is possible, minimizing the catalytic loss due to surface poisoning.     

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.