Preparation and electrochemical analysis of graphene/polyaniline composites prepared by aniline polymerization

Polyaniline (PANI)/graphene nanosheet (GNS) composites were prepared by a chemical oxidation polymerization. The morphology, structure, and crystallinity of the composites were examined by scanning electron microscopy, transition electron microscopy, and X-ray diffraction. Electrochemical properties were characterized by cyclic voltammetry in 1 M H₂SO₄ electrolyte. GNS are considered as supporting materials which can provide a large number of active sites. The PANI nanofibers with diameter of 50 nm were homogeneously coated on the surface of GNS. The PANI/GNS composites exhibited a better electrochemical performance than the pure individual components. The PANI/GNS composites showed the highest specific capacitance 923 Fg^?1 at 10 mVs^?1 compared to 465 Fg^?1 for pure PANI and 99 Fg^?1 for GNS.     

苯胺的电化学聚合计时电流方程式

本文提出了苯胺的电化学聚合计时电流方程式, 并进行了验证。浓度为1.10mol.dm^-^3苯胺(内含2.2mol.dm^-^3HCl)溶液在铂圆盘电极上进行电化学聚合反应, 理论与实验相符。     

Electrochemical polymerization of aniline in phosphoric acid

The electrochemical synthesis of common conductive polymers such as polyaniline in phosphoric acid is a little different from that in other acidic media such as sulfuric acid. Electropolymerization in phosphoric acid is difficult, and this electrolyte medium is not applicable for this purpose. However, it is possible to overcome this problem by the addition of a small amount of sulfuric acid. In this case, the electropolymerization process can be successfully performed when the phosphate ion is doped. For instance, polyaniline films electrodeposited from an electrolyte solution of phosphoric acid have good stabilities and useful morphologies. Interestingly, phosphate doping results in the formation of nanostructures, whereas the polymer surface is macroscopically smooth. In an appropriate ratio, a mixed electrolyte of H₃PO₄ and H₂SO₄ can be used for the electropolymerization of aniline; thus, H₂SO₄ acts as a required agent for successful polymer growth, and H₃PO₄ acts as a doping agent. In this case, a small amount of sulfate is incorporated into the polymer matrix, which does not participate in the electrochemical insertion/extraction process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3304–3311, 2006     

Conducting polystyrene/polyaniline blend through template-assisted emulsion polymerization

Electrically conducting polystyrene (PS)/polyaniline blends have been prepared through a one-step “anilinium-surfactant template”-assisted emulsion polymerization at room temperature. The self-assembled cylindrical An⁺PDPSA^? micelle formed inside the PS matrix can act as a structure directing template cum dopant. Morphological observation under scanning electron microscopic studies revealed that during the progress of polymerization, the initially formed nanostructured conducting polyaniline was changed into cubic/hexagonal/lamellar particles and finally transformed into a percolated structure inside the PS matrix. Blend was further characterized by UV-Vis spectroscopy, FTIR spectroscopy, X-ray diffraction, electrical conductivity, thermal stability, dielectric property, rheological property, and electromagnetic shielding efficiency. The key finding of this work is that the conductive blend prepared through micelle-guided polymerization exhibited superior electrical conductivity (9.6 S/m) with low percolation threshold concentration (5 wt%), excellent thermal stability, electromagnetic interference (EMI) SE of 1–10 dB which makes it a promising candidate for EMI shielding and antistatic discharge matrix for the encapsulation of microelectronic devices.     

In situ polymerized polyaniline films. 4. Film formation in dispersion polymerization of aniline

Polyaniline films were grown on glass supports during dispersion polymerizations of aniline using poly(N-vinylpyrrolidone) and hydroxypropylcellulose as stabilizers. The initiation of polyaniline chains is proposed to be heterogeneously catalyzed by the surfaces immersed in the reaction mixture. Film formations in dispersion and precipitation polymerizations are compared. Surfometry and optical absorption were used to assess the submicrometer film thickness, and FTIR spectroscopy was used to analyze the chemical structure of films and prove the absence of stabilizer. The film thickness was proportional to the dimensions of simultaneously produced colloidal polyaniline particles. The conductivity of films increased with increasing film thickness.     

Polymerization of aniline on polyaniline membranes

When solutions of aniline hydrochloride and ammonium peroxydisulfate were separated by a semipermeable cellulose membrane, the reactants met at the membrane and produced a polyaniline (PANI) membrane at the interface. The oxidative polymerization of aniline then proceeded in situ on the PANI-cellulose composite membrane. PANI was produced entirely at the monomer side of the membrane; about 80% conversion of aniline to PANI was observed after 24 h. The oxidation of aniline with peroxydisulfate consists in the transfer of electrons from aniline to the oxidant; it is proposed that electrons pass through the PANI membrane, which is conducting, and electroneutrality is maintained by the simultaneous transfer of protons. The reaction between aniline and peroxydisulfate thus takes place without the need for both reactant molecules to be in physical contact. The residual aniline is located only at its original side of the membrane, but the product of ammonium peroxydisulfate conversion, ammonium hydrogen sulfate, was found on both sides of the membrane. Fourier-transform infrared spectroscopy has been used to analyze PANI, the reaction residues and byproducts, and to prove that PANI is protonated with counter-ions of the sulfate type. Using this technique, we have detected only small differences in the molecular structure of PANI prepared with the membrane-separated reactants and in the polymerization when reactants were mixed; also, the molecular weights differed only marginally. The conductivity of both types of PANI was about the same. The repeated polymerization of aniline on the earlier prepared PANI-cellulose membrane yielded similar results, thus confirming the proposed concept of coupled electron- and proton-transfer through the PANI membrane.     

Crystallization and polymerization of 6-aminocaproic acid as simultaneous processes

Vapor of 6-aminocaproic acid (ACA) at a pressure of 0.12 mm Hg was observed to polymerize when placed in the presence of different types of surfaces, crystalline and amorphous, at temperatures around 170°C. Two clearly distinct stages of the process could be detected. The first was an induction period, during which the polymer phase must be nucleated. The length of this nucleation stage depended on factors not well understood. In the second stage, polymer was produced at a constant rate which seemed to be related to the vapor pressure of ACA. The polymer produced consisted of the characteristic radiating arrays of ribbonlike crystals known as spherulites. The spherulites, in turn, were made up of primary and secondary lamellae about 90 Å thick. Electron diffraction studies showed that the polymer chains were folded within the lamellae. Further it was proved by chemical and crystallographic arguments that adsorption and polymerization should be simultaneous processes.     

RF-plasma polymerization and characterization of polyaniline

Suitable modifications are done in a RF sputtering set up to facilitate synthesis of polyaniline thin film by RF-plasma polymerization process. The synthesized films are characterized by FTIR, XRD, Ellipsometry, UV-visible absorption & reflection and SEM. The films prepared are highly cross-linked, amorphous in nature and have band gap of 2.07 eV. SEM images show the uniformity in film morphology. The refractive index of the films is determined to be 1.11 and dielectric constant is 1.12 at a wavelength 620 nm in the visible region.     

Indirect electrochemical oxidation of aniline in acid electrolyte with active oxygen species

Kinetics and selectivity of the aniline oxidation on a boron-doped diamond electrode and lead dioxide anode (Pb/PbO₂) in an acid electrolyte were studied under various generation conditions of active oxygen species. The resulting kinetic dependences can be described by a pseudo-first-order equation. The apparent rate constants of the process were determined for two electrolysis modes: direct anodic oxidation and oxidation with addition of hydrogen peroxide. UV spectroscopy was used to determine that the aniline destruction process occurs via formation of a number of intermediate products (benzoquinone, carboxylic acids). It was shown that the aniline destruction process can occur with a rather high efficiency (~80–90%) on the electrode types under study.     

Transparent and conductive thin films of graphene/polyaniline nanocomposites prepared through interfacial polymerization

This communication reports a simple, one-pot procedure for the synthesis and processing of transparent and conductive thin films of graphene/polyaniline nanocomposites based on an interfacial polymerization. Thin films presenting transmittance of 89% and sheet resistance of 60.6 ? sq(-1) are spontaneously obtained and can be easily transferred to suitable substrates.     

Matrix polymerization of aniline in the presence of polyamides containing sulfo acid groups

The matrix synthesis of polyaniline in the presence of water-soluble aromatic polyamides containing sulfo acid groups has been studied. It has been shown that the nature of polyacid and the concentration of reagents affect the shape and dynamics of a change in absorption spectra. The S-shaped profile of kinetic curves for spectra variation and the experiments on the seed polymerization provide evidence for the autocatalytic character of polymerization. It has been concluded that, depending on the nature of polyacid, polymer complexes form in which polyaniline macromolecules are situated along main chains of polyacid macromolecules (the two-stream structure) or appear as side chains of polyacid macromolecules (the comb-shape structure). In the latter case, polyaniline macromolecules serve as ionic bridges crosslinking polyacid macromolecules, as is confirmed by the viscometric study of solutions in the course of polymerization.     

Self-assembly of aniline oligomers and their induced polyaniline supra-molecular structures

Aniline chemical oxidative polymerisation (COP), which produces various polyaniline (PANI) and oligoaniline supra-molecular structures, can be regarded as an in situ self-assembly process. This review provides a brief introduction to recent work on the structural characters and self-assembly behaviours of oligomeric aniline chemical oxidation products; it is focused on the relationships between the oligomeric species and morphology of the final products such as PANI nanoparticles, nanofibres/rods, nanotubes or oligoaniline nanosheets, micro/nanospheres in aniline COP systems. Several mechanisms proposed as explanations for the formation of typical supra-molecular structures are discussed in order to illustrate the roles of aniline oligomers. This article concludes with our perspectives on future work remaining to be done to uncover the formation mechanism of supra-molecular structures constructed by aniline chemical oxidation products and their controllable synthesis.     

Electrochemical polymerization of polyaniline doped with Zn2+ as the electrode material for electrochemical supercapacitors

Polyaniline doped with Zn²⁺ (PANI/Zn²⁺) films was synthesized by cyclic voltammetric method on stainless steel mesh substrates in 0.2 mol L^?1 aniline and 0.5 mol L^?1 sulfuric acid electrolyte with various concentrations of zinc sulfate (ZnSO₄·7H₂O). The structure and morphology of PANI and PANI/Zn²⁺ films were characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques, respectively. The electrochemical properties of PANI and PANI/Zn²⁺ films were investigated by cyclic voltammetry, galvanostatic charge–discharge test, and electrochemical impedance spectroscopy in 0.5 mol L^?1 H₂SO₄ electrolyte in a three-electrode system. The results show that the surface morphology of PANI/Zn²⁺ is more rough than that of pure PANI. The specific capacitance of the PANI/Zn²⁺ film displays a larger specific capacitance of 738 F g^?1, lower resistance, and better stability as compared with the pure PANI film. Thus, good capacitive performance demonstrates its potential superiority for supercapacitors.     

Enzymatically synthesized polyaniline film deposition studied by simultaneous open circuit potential and electrochemical quartz crystal microbalance measurements

The chemical and enzymatic deposition of polyaniline (PANI) films by in situ polymerization was studied and the resulting films were characterized. The film formation and polymerization processes were simultaneously monitored by the evolution of the open circuit potential and quartz-crystal microbalance measurements. Different substrates, such as Indium-Tin oxide electrodes and gold-coated quartz-crystal electrodes were used as substrates for PANI deposition. Electroactive PANI films were successfully deposited by in situ enzymatic polymerization at low oxidation potential. The electrogravimetric response of the enzymatically deposited PANI film was studied by cyclic voltammetry in monomer-free acidic medium. The morphology of the films was observed by scanning electron microscopy, revealing a granular structure in enzymatically deposited PANI. The PANI films were also characterized by thermogravimetric analysis, electrochemical impedance spectroscopy, and X-ray photoelectron and Fourier-transformed infrared spectroscopy. The simultaneous use of quartz crystal microbalance and open circuit potential is presented as a very useful technique to monitor enzymatic reactions involving oxidoreductases.     

Exploiting micellar environment for simultaneous electrochemical determination of ascorbic acid and dopamine

A simple and reliable method for simultaneous electrochemical determination of ascorbic acid (AA) and dopamine (DA) is presented in this work. It was based on the use of the cationic surfactant cetylpyridinium chloride (CPC) that enables the separation of the oxidation peaks potential of AA and DA. Cyclic voltammetry (CV) as well as pulse differential voltammetry (PDV) were used in order to verify the voltammetric behaviour in micellar media. In the cationic surfactant CPC, a remarkable electrostatic interaction is established with negatively charged AA, as a consequence, the oxidation peak potential shifted toward less positive potential and the peak current increased. On the other hand, the positively charged DA is repelled from the electrode surface and the oxidation peak potential shifts toward more positive potential in comparison to the bare electrode. Therefore, the common overlapped oxidation peaks of AA and DA can be circumventing by using CPC. Parameter that affects the E_pa and I_pa such as CPC concentration and pH were studied. Under optimised conditions, the method presented a linear response to AA and DA in the concentration range from 5 to 75 μmol L⁻¹ and 10 to 100 μmol L⁻¹, respectively. The proposed method was successfully applied to the simultaneous determination of AA and DA in dopamine hydrochloride injection (DHI) samples spiked with AA.     

Electrochemical polymerization of aniline in SDS admicelles

The electrochemical polymerization of aniline was studied in sodium dodecyl sulfate (SDS) admicelles. The results demonstrate that electrochemical polymerization of aniline can be catalyzed by admicelles. The catalytic efficiency in SDS solutions increased slowly with SDS concentration when the SDS concentration was very low, but increased rapidly when SDS admicelles formed on the electrode surface. The catalytic efficiency decreased with the addition of n-pentanol. The polyaniline films formed in SDS admicelles were nanometer films and the size of particles in the films increased with SDS concentration, but decreased with the addition of n-pentanol. Therefore, n-C₅H₁₁OH can be used to regulate the electrochemical polymerization of aniline in SDS admicelles.     

Electrochemistry of conductive polymers 40. Earlier phases of aniline polymerization studied by Fourier transform electrochemical impedance spectroscopy

Earlier stages of aniline polymerization have been studied by Fourier transform electrochemical impedance spectroscopy (FTEIS) experiments. Initial oxidation of aniline leads to the formation of a thin layer passivating the electrode surface, which is depassivated upon a further increase in potential and mediates a further electron transfer from aniline to the electrode. The charge-transfer resistance was first shown to decrease upon increasing the potential, which leads to the inductive behavior upon further increase in the overpotential. The oligomer-polymer film thus formed was shown to undergo a transition from its passive state to neutral oligomer-polymer molecules via a conducting state; its oxidation was then observed during the anodic scan. It is this transition to the conductive states that leads to the propagation of the conductive zone throughout the nonconductive film, leading to further growth of polyaniline, as was clearly shown by the FTEIS measurements.     

Consideration of interface polarization in the modeling of dielectric property for ethylene vinyl acetate (EVA)/polyaniline conductive composites prepared through in-situ polymerization of aniline in EVA matrix

In this study conductive composite of ethylene vinyl acetate (EVA)/polyaniline (Pani) were prepared by in-situ polymerization technique. Dielectric properties (Permittivity) of the composites have been investigated with respect to concentration of Pani and frequency of electric field. For predicting permittivity of the composites, different mixing rules proposed by Lichtenecker, Bruggeman, Jaysundere–Smith, Maxwell–Wagner, and Yamada have been verified at 10, 10³, and 10⁶ Hz frequencies. It has been found that the theoretical permittivities predicted by different models differ largely from experimental permittivity when measured at 10 and 10³ Hz frequencies. The limitations of the models as well as the cause of deviations between the theoretically predicted and experimentally observed results have been discussed. A new model for permittivity has been proposed by considering the generation of interface polarization between the EVA matrix and Pani particles. This model fits well with the experimentally observed results.