Conducting polymers (CPs) have received much attention in both fundamental and practical studies because they have electrical and electrochemical properties similar to those of both traditional semiconductors and metals. CPs possess excellent characteristics such as mild synthesis and processing conditions, chemical and structural diversity, tunable conductivity, and structural flexibility. Advances in nanotechnology have allowed the fabrication of versatile CP nanomaterials with improved performance for various applications including electronics, optoelectronics, sensors, and energy devices. The aim of this review is to explore the conductivity mechanisms and electrical and electrochemical properties of CPs and to discuss the factors that significantly affect these properties. The size and morphology of the materials are also discussed as key parameters that affect their major properties. Finally, the latest trends in research on electrochemical capacitors and sensors are introduced through an in-depth discussion of the most remarkable studies reported since 2003.

Electrical and Electrochemical Properties of Conducting Polymers.

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

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

The course of aniline oxidation with ammonium peroxydisulfate in aqueous solutions has been investigated The reaction was terminated at various times and the intermediates collected Besides the precipitates, the films deposited in situ on silicon windows have also been studied The kinetic course of polymerization is controlled by the acidity level, which changes during the polymerization from pH 8 to a final value close to pH 1 It has two distinct exothermic phases Gel-permeation chromatography indicates that aniline oligomers are produced at first at high pH, while polyaniline follows after the pH becomes sufficiently low The growth of polyaniline nanotubes was observed by optical microscopy and confirmed by electron microscopy The molecular structure of the reaction intermediates was studied in detail by FTIR spectroscopy Oxidation products are markedly sulfonated, and they contain phenazine units Aniline oligomers are more soluble in chloroform than the polymer fraction, which contains nanotubes

Evolution of polyaniline nanotubes: The oxidation of aniline in water

Using Fourier Transform InfraRed (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM), we characterize the structure and/or morphology of hematite (α-Fe2O3) particles with sizes of 7, 18, 39 and 120 nm. It is found that these nanoparticles possess maghemite (γ-Fe2O3)-like defects in the near surface regions, to which a vibrational mode at 690 cm−1, active both in FTIR and Raman spectra, is assigned. The fraction of the maghemite-like defects and the net lattice disorder are inversely related to the particle size. However, the effect is opposite for nanoparticles grown by sintering of smaller hematite precursors under conditions when the formation of a uniform hematite-like structure throughout the aggregate is restricted by kinetic issues. This means that not only particle size but also the growth kinetics determines the structure of the nanoparticles. The observed structural changes are interpreted as size-induced α-Fe2O3
				↔
				γ-Fe2O3 phase transitions. We develop a general model that considers spinel defects and absorbed/adsorbed species (in our case, hydroxyls) as dominant controls on structural changes with particle size in hematite nanoparticles, including solid-state phase transitions. These changes are represented by trajectories in a phase diagram built in three phase coordinates—concentrations of spinel defects, absorbed impurities, and adsorbed species. The critical size for the onset of the α
				→
				γ phase transition depends on the particle environment, and for the dry particles used in this study is about 40 nm. The model supports the existence of intermediate phases (protohematite and hydrohematite) during dehydration of goethite. We also demonstrate that the hematite structure is significantly less defective when the nanoparticles are immersed in water or KBr matrix, which is explained by the effects of the electrochemical double layer and increased rigidity of the particle environment. Finally, we revise the problem of applicability of IR spectroscopy to the lattice vibrations of hematite nanoparticles, demonstrating that structural comparison of different samples is much more reliable if it is based on the Eu band at about 460 cm−1 and the spinel band at 690 cm−1, instead of the A2u/Eu band at about 550 cm−1 used in previous work. The new methodology is applied to analysis of the reported IR spectra of Martian hematite.

Size-dependent structural transformations of hematite nanoparticles. 1. Phase transition.

Aniline was oxidized with ammonium peroxydisulfate in solutions of strong acid (0.1 M sulfuric acid), weak acid (0.4 M acetic acid), or alkali (0.2 M ammonium hydroxide). The properties of the oxidation products and their morphology are controlled by the initial acidity of the medium and the acidity profile during the oxidation; the acidity increases because sulfuric acid is a byproduct. Conducting polyaniline nanogranules, nanotubes, or nonconducting oligoaniline microspheres were obtained, respectively. FTIR spectra suggest that the oligomers produced by the oxidation of neutral aniline molecules at the beginning of oxidation are similar, regardless of the acidity of the medium. Neutral aniline molecules, prevailing under alkaline conditions, are easily oxidized to aniline oligomers composed of ortho- and para-coupled aniline constitutional units. Ortho-coupled units are further converted by oxidative intramolecular cyclization to phenazines. It is proposed that, in acidic media, N-phenylphenazine units...

Oxidation of Aniline: Polyaniline Granules, Nanotubes, and Oligoaniline Microspheres

Swelling and volume changes of polyaniline upon redox switching

Electropolymerization of 2-methoxy aniline. Electrochemical and spectroscopical product characterization

Binding of Pb(II) in the system humic acid/goethite at acidic pH.

The binding of Pb(II) to humic acids is studied through an approach combining equilibrium and spectroscopic measurements. The methods employed are potentiometric and fluorometric titrations, fluorescence excitation–emission matrices (EEM) and IR spectroscopy. Potentiometric titration curves are analyzed using the NICA equations and an electrostatic model treating the humic particles as an elastic polyelectrolyte network. EEMs are analyzed using parallel factor analysis, decomposing the signal in its independent components and finding their dependence on Pb(II) activity. Potentiometric results are consistent with bimodal affinity distributions for Pb(II) binding, whereas fluorometric titrations are explained by monomodal distributions. EEM analysis is consistent with three independent components in the humic fluorescence response, which are assigned to moieties with different degree of aromaticity. All three components show a similar quenching behavior upon Pb(II) binding, saturating at relatively low Pb(I...

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Pb(II) binding to humic substances: an equilibrium and spectroscopic study.

The quasi-equilibrium electrochemomechanical behavior of relatively thick polyaniline films in sulfuric acid is investigated through experimental measurements and theoretical modeling. The leucoemeraldine (LE)-emeraldine (EM) conversion, or redox switching, is studied. The dependence of film volume and electrochemical charge is determined as a function of applied potential. It is observed that the film volume follows the charge, showing an expansion during the second half of the LE-EM oxidation. The model postulates the existence of a stable intermediate, protoemeraldine (PE), with a formal potential distribution for the PE-EM reaction. The volume change is modeled statistically considering contributions from mixing, polymer deformation, and electrostatic charge. The model shows very good agreement with the experiments, indicating that, in the conditions studied, the deformation contribution dominates the volume changes as a result of the conformational modifications undergone by the polymer in the PE-EM oxidation.

Estela María Andrade

Papers

Swelling and volume changes of polyaniline upon redox switching

Electropolymerization of 2-methoxy aniline. Electrochemical and spectroscopical product characterization

Binding of Pb(II) in the system humic acid/goethite at acidic pH.

Pb(II) binding to humic substances: an equilibrium and spectroscopic study.

Quasi-equilibrium volume changes of polyaniline films upon redox switching. Formal potential distribution and configurational modeling.