Formation of nanostructured polyaniline by dopant-free oxidation of aniline in a water/isopropanol mixture

Nanostructured polyaniline (PANI) was synthesised by the oxidation of aniline in a water/ isopropanol (propan-2-ol, IPA) (50 vol. %) mixture, without added acid, using ammonium peroxydisulfate (APS) as an oxidant. Influence of the IPA co-solvent and the reaction time on the molecular structure, morphology and properties of synthesised PANI samples was studied by FTIR, Raman, and UV-VIS spectroscopies, scanning and transmission electron microscopies (SEM and TEM), and conductivity measurements. The course of the reaction was followed by monitoring changes in the temperature and acidity of the reaction medium. The results were compared with those obtained for PANI prepared in water without IPA under the same reaction conditions. The importance of the solvation effects, dielectric constant of the solvent, and the enthalpy of mixing of IPA with water on the course of the polymerisation reaction and on the properties of polymeric products in the water/IPA medium in comparison with those in water was pointed out.     

Spectroscopy of thin polyaniline films deposited during chemical oxidation of aniline

Any surface immersed in the aqueous reaction mixture used for the preparation of polyaniline becomes coated with a polyaniline film of submicrometre thickness. In this way, various materials can be modified by an overlayer of conducting polymer. The present review illustrates the role of infrared, Raman, and UV-VIS spectroscopies in the studies of polyaniline film growth. Spectroscopic methods are crucial in the evaluation of the performance of polyaniline films alone or in combination with nanoparticles of noble metals. The assessment of film ageing and stability can be followed conveniently by these methods. Carbonization of polyaniline films to nitrogen-containing carbon analogues is also discussed.     

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.     

Effect of aromatic substitution in aniline on the properties of polyaniline

Substitution in aniline has tremendous effect in the synthesis of poly(substituted anilines) as well as in their properties. In this investigation polyaniline (PANI), poly(m-nitro aniline) (PMNA), poly(m-amino phenol) (PMAP) and poly(o-ethyl aniline) (POEA) were synthesized by oxidative polymerization under identical conditions. Different properties were measured and compared with PANI to find out the presence of electron donating -OH group, electron withdrawing -NO₂ group and less effecting ethyl group on the properties of poly(substituted anilines). It was found that presence of any type of substitution in the benzene ring of aniline increases the solubility of the resulted polymer but reduces the yield, degree of polymerization, thermal stability, electrical and thermal conductivity. The colors, bulk density, particle size, percentage of crystallinity vary considerably depending on the nature of substitution.     

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.     

A sensor based on polyaniline nanofibers/ionic liquid-functionalized carbon nanotubes composite for electrocatalytic oxidation of guanine

In this paper, a novel polyaniline (PANI) nanofibers/ionic liquid-functionalized carbon nanotubes (IL-CNTs) composite-modified electrode was prepared, and its application on electrocatalytic oxidation of guanine of sequence-specific DNA was investigated. The surface morphology and the related electrochemical behaviors of the PANI/IL-CNTs composite film were characterized with scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry, respectively. The PANI/IL-CNTs composite showed a good response current toward the direct electrooxidation of ssDNA due to the synergistic effect between PANI nanofibers and IL-CNTs. Based on this, it was adopted as an excellent sensing platform for highly sensitive determination of guanine. The detection limit was 3.1 × 10^?9 mol/L.     

Preparation of highly conductive, self-assembled gold/polyaniline nanocables and polyaniline nanotubes

One-dimensional gold/polyaniline (Au/PANI-CSA) coaxial nanocables with an average diameter of 50-60 nm and lengths of more than 1 mum were successfully synthesized by reacting aniline monomer with chlorauric acid (HAuCl(4)) through a self-assembly process in the presence of D-camphor-10-sulfonic acid (CSA), which acts as both a dopant and surfactant. It was found that the formation probability and the size of the Au/PANI-CSA nanocables depends on the molar ratio of aniline to HAuCl(4) and the concentration of CSA, respectively. A synergistic growth mechanism was proposed to interpret the formation of the Au/PANI-CSA nanocables. The directly measured conductivity of a single gold/polyaniline nanocable was found to be high (approximately 77.2 S cm(-1)). Hollow PANI-CSA nanotubes, with an average diameter of 50-60 nm, were also obtained successfully by dissolving the Au nanowire core of the Au/PANI-CSA nanocables.     

Modified polyaniline through simultaneous electrochemical polymerization of aniline and metanilic acid

Simultaneous electropolymerization of aniline and metanilic acid in aqueous HClO₄ leads to a copolymer similar to that obtained by direct sulfonation of polyaniline. Characterization by electrochemical and spectroscopic methods (UV -visible, Fourier transform IR and proton NMR) indicated the presence of polyaniline linear chains in which metanilic acid units were inserted as spacers. Elemental analysis showed that the copolymer was 40% doped by the sulfonate side-groups intramolecularly (self-doping) and 20% doped by ClO₄⁻ intermolecularly. The presence of sulfonate functional groups decreased electronic conductivity and increased solubility in alkaline solvents, but the electtrochemical properties remained principally that of polyaniline.     

Effect of aniline formaldehyde resin on the conjugation length and structure of doped polyaniline: Spectral studies

A DBSA (n‐dodecylbenzene sulfate)‐complexed aniline formaldehyde [AF(DBSA)_1.0] was successfully synthesized with excess aniline (compared with formaldehyde) in the presence of n‐dodecylbenzene sulfonic acid (HDBSA), which was complexed with aniline monomer before polymerization. The resin was carefully characterized with ¹H and ¹³C NMR, electron spectroscopy for chemical analysis, and Fourier transform infrared and was demonstrated to be a polymer in which anilines were all complexed with HDBSA and became anilinium salts. A drastic decrease of the maximum absorption wavelength (ultraviolet–visible spectra) of DBSA‐doped polyaniline [PANI(DBSA)_0.5] was found when AF(DBSA)_1.0 was mixed, and this resulted from the reduced conjugation length. A similar effect on PANI(DBSA)_0.5 was found when free HDBSAs were mixed with PANI(DBSA)_0.5. Visual inspection with an optical microscope revealed that PANI(DBSA)_0.5/AF(DBSA)_1.0 gave uniform morphologies in various compositions, showing possible miscibility for this system. X‐ray diffraction patterns of PANI(DBSA)_0.5/AF(DBSA)_1.0 showed that the layered structure of PANI(DBSA)_0.5 was still present but became shorter in the polyblend because of the presence of AF(DBSA)_1.0. Solid‐state ¹³C NMR spectra revealed that the reduced conjugation length was derived from the interaction of alkyl groups between HDBSA, complexed DBSA, and dopant DBSAs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3116–3125, 2005     

The conversion of polyaniline nanotubes to nitrogen-containing carbon nanotubes and their comparison with multi-walled carbon nanotubes

Polyaniline (PANI) nanotubes were prepared by the oxidation of aniline in solutions of acetic or succinic acid, and subsequently carbonized in a nitrogen atmosphere during thermogravimetric analysis running up to 830 °C. The nanotubular morphology of PANI was preserved after carbonization. The molecular structure of the original PANI and of the carbonized products has been analyzed by FTIR and Raman spectroscopies. Carbonized PANI nanotubes contained about 8 wt.% of nitrogen. The molecular structure, thermal stability, and morphology of carbonized PANI nanotubes were compared with the properties of commercial multi-walled carbon nanotubes.     

流动注射化学发光法测定水中的苯胺

基于在多聚磷酸介质中,KMnO4氧化苯胺能产生强化学发光,建立了流动注射化学发光测定苯胺的新方法.在优化条件下,化学发光强度ⅠCL与苯胺的浓度在2.0×10～1.0×10-6 mol/L范围内呈良好的线性关系,回归方程为ⅠCL=63.11 2.37×108c(r=0.9997,n=9),检出限为5.0×10-10 mol/L,对1.0×10-7 mol/L苯胺进行11次测定,其相对标准偏差为0.8%(n=11).已用于环境水体中苯胺的测定,回收率在95.1%～105.1%之间.     

苯胺在碳纳米管上的吸附特征

苯胺是一种重要的有机化工原料,能通过皮肤和呼吸道进入人体而引起中毒,还会严重污染环境。目前,国内外处理含苯胺废水的方法主要有氧化法、萃取法、生化法、吸附法等。本文使用碳纳米管进行液相吸附除去苯胺。     

Nanostructured aniline oxidation products: self-assembled films at the air/liquid interface

With the use of the "falling pH" approach, the free floating films obtained at the air/liquid interface during aniline oxidative polymerization in the presence of hydrochloric acid have been reported and characterized for the first time. The surface of the films is compact and consists of small densely packed particles (around 10-20 nm in diameter). In addition to the free floating films the precipitation of various self-assembled nanostructures was also observed. The thickness of the films depends on the concentration of the reactants and ranges from 40 to 50 nm. Scanning electron microscopy (SEM) and transmission electron microscopy results imply that 3D nanostructures are physically adsorbed onto the film and that they represent two separated phases. Fourier transform infrared (FTIR) and UV-vis measurements have confirmed the presence of polyaniline and branched oligoanilines. On the basis of an orientation distribution of H(2)O and aniline molecules at the air/liquid interface and with the use of the cooperative effect of hydrogen-bond formation, a mechanism for film growth has been proposed. Three samples are synthesized in the presence of different acids-nitric, sulfuric, and acetic. The SEM and FTIR data showed similar morphologies and structural characteristics. This implies that the morphology and structure of the final products depend on the acidity conditions (pH) during the reaction rather than on the nature of the dopant acid.     

Conducting poly(aniline) nanotubes and nanofibers: controlled synthesis and application in lithium/poly(aniline) rechargeable batteries

The primary aim of this work was to synthesize aligned perchloric-acid-doped poly(aniline) (HClO(4)-doped PANI) nanotubes by a simple alumina template method and to investigate their application in lithium/poly(aniline) rechargeable batteries. Powder X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) analysis were used to characterize the nanostructures obtained. The second aim addressed the preparation of HClO(4)-doped PANI microspheres and nanofibers on a large scale through a modified spraying technique, since the template synthesis has limitations in mass production. The present synthesis methods are simple and can be extended to the preparation of a broad range of one-dimensional conductive polymers. Furthermore, electrochemical measurements showed that the as-prepared HClO(4)-doped PANI nanotubes exhibit better electrode performances than their commercial counterparts because they possess more active sites, higher conductivity, and relative flexibility. This indicates that HClO(4)-doped poly(aniline) nanomaterials are promising in the application of lithium/polymer rechargeable batteries.     

Activation effect of nickel phosphate co-catalysts on the photoelectrochemical water oxidation performance of TiO2 nanotubes

We present exemplary fabrications of controlled Nickel phosphate (NiPi)/TiO₂ nanotubes arrays (TNTs) in phosphate buffer for boosted photoelectrochemical (PEC) water splitting. The TNTs/NiPi composite electrodes revealed a considerably enhanced photocurrent density of 0.76 mA/cm², up to 3-time enhancements than bare TNTs, mostly because of the enhanced charge separation, decreased carrier recombination, and improving kinetics of the water oxidation. Also, we demonstrated that the NiPi can assist the PEC features of TNTs over a varied region of pH values from 1 to 14. Incorporation of NiPi over the TNTs surface advances the light absorption features of the electrode, resulting in an enhanced photogenerated charge carrier; and promotes the reactive sites for water oxidation, which was proved by the double-layer capacitance. The TNTs/NiPi photoelectrode exhibited excellent photostabilization under continuous illumination for 5 h, and the photoconversion efficiencies were 0.45%, 3-fold enhancements than with bare TNTs under the illuminations. Overall, this work might offer an innovative approach to fabricating and designing efficient electrodes with superior contact interfaces among photoanodes and numerous co-catalysts.     

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.     

Electrochemical behavior of polyaniline synthesized by chemical oxidation

The slow voltammetry was taken on the paste electrode consisting of polyaniline powder and Teflon binder which was applied to pyrographite disc electrode. The potential cycle range was +0.6V→ ? 0.2V→+0.8V→+0.6V vs. SCE. It was found that the voltammetry curves are similar for both polyanilines obtained chemically and electrochemically. The difference of the voltammetry curves in various acids might be attributed to some exchange of doping anions in polyaniline. The first redox couple peaks shifted to positive potential direction with increase of pH and it might be associated with the proton addition-elimination reaction. It was shown that polyaniline prepared from very dilute or concentrated acid solution was electrochemically inactive.     

Pyridiniumchlorochromate oxidations: Studies on the kinetics and substituent effect in the oxidation of aniline in nonaqueous systems

Pyridiniumchlorochromate (PCC) oxidizes aniline and substituted anilines except nitro anilines smoothly in chlorobenzene–nitrobenzene mixtures in the presence of dichloroacetic acid. The reaction has unit dependence on each of the aniline, PCC, and dichloroacetic acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electronwithdrawing groups retard the reaction, and the rate data obey Hammett's relationship. The reaction constant ρ is -3.75. Azobenzene and p-benzoquinone have been obtained as products. The observed experimental data have been rationalized in terms of the formation of an intermediate complex involving PCC–amine undergoing a rapid decomposition to products.     

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.