Electronically conductive polyanilines

Electronically conductive polyaniline has been paid much attention as a potential membrane material for gas separation because of high selectivity, particularly very high selectivity of oxygen over nitrogen (1-4), In addition, it is thermally stable and soluble in NMP, not like common electronically conductive polymers such as... 

The HRP-catalyzed polymerization of phenols was found to be a convenient way to produce redox polymers and conducting (electronically conducting and ionically conducting) polymers. Besides the interest in electronic conductive polyanilines [121], many efforts have been made to produce ionically conductive phenol polymers for battery applications. A classic effort is the synthesis of poly(hydroquinone) for use as a redox polymer. Typically, poly(quinone)s are prepared via chemical or electrochemical methodologies [122,123]. Both processes produce a large amount of by-products and lead to complex polymer structiues. The first alternative pathway to produce poly(hydroquinone) by peroxidase catalysis was based on a multienzymic... 

A second type of soHd ionic conductors based around polyether compounds such as poly(ethylene oxide) [25322-68-3] (PEO) has been discovered (24) and characterized. These materials foUow equations 23—31 as opposed to the electronically conducting polyacetylene [26571-64-2] and polyaniline type materials. The polyethers can complex and stabilize lithium ions in organic media. They also dissolve salts such as LiClO to produce conducting soHd solutions. The use of these materials in rechargeable lithium batteries has been proposed (25). 

Conducting Polymers Electronically conducting polymers (such as polypyrrole, polythiophene, and polyaniline) have attracted considerable attention due to their ability to switch reversibly between the positively charged conductive state and a neutral, essentially insulating, form and to incorporate and expel anionic species (from and to the surrounding solution), upon oxidation or reduction ... 

Nucleation models have also been invoked for the oxidation of polyaniline films.209,213 In both cases, the nucleation of electronically conductive zones was assumed, following Aoki s well-documented model. The possibility that the nucleation of ionically conductive regions could be rate limiting does not appear to have been considered. 

Another convenient way to disperse platinum-based electrocatalysts is to use electron-conducting polymers, such as polyaniline (PAni) or polypyrrole (PPy), which play the role of a three-dimensional electrode.In such a way very dispersed electrocatalysts are obtained, with particle sizes on the order of a few nanometers, leading to a very high activity for the oxidation of methanol (Fig. 10). 

In view of the complexity of the material, it is difficult to unequivocally assign a particular mechanism for electronic conduction in the polymer, although some evidence exists to suggest that it involves three-dimensional variable-range hopping as found for other polymers [213], It has also been suggested that the conductivity of polyaniline is a combination of both ionic and electronic conductivity [207], and is... 

Electronically conducting polymers (ECPs) such as polyaniline (PANI), polypyrrole (PPy) and po 1 y(3.4-cthy 1 cncdi oxyth iophcnc) (PEDOT) have been applied in supercapacitors, due to their excellent electrochemical properties and lower cost than other ECPs. We demonstrated that multi-walled carbon nanotubes (CNTs) prepared by catalytic decomposition of acetylene in a solid solution are very effective conductivity additives in composite materials based on ECPs. In this paper, we show that a successful application of ECPs in supercapacitor technologies could be possible only in an asymmetric configuration, i.e. with electrodes of different nature. 

As our quantum-chemical calculations show, similar transformation and delocalization of bonds takes place in the conductive forms of some other types of CPs (polyaniline, polypyrolle, etc.). Delocalization of chemical bonds after activation leads to appearance of an electronic conductivity in such types of conducting polymers and creates prerequisites for their application as electrode materials of electrochemical power sources. Such activation can be stimulated by intercalation of ions, applying the potential, and by use of some other low energetic factors. 

Transition metal compounds, such as organic macrocycles, are known to be good electrocatalysts for oxygen reduction. Furthermore, they are inactive for alcohol oxidation. Different phthalocyanines and porphyrins of iron and cobalt were thus dispersed in an electron-conducting polymer (polyaniline, polypyrrole) acting as a conducting matrix, either in the form of a tetrasulfonated counter anion or linked to... 

Boyle A, Genies EM, Lapkowski M. Application of electronic conducting polymers as sensors— polyaniline in the solid-state for detection of solvent vapors and polypyrrole for detection of biological ions in solutions. Synth Met 1989 28 C769-C774. 

Polyaniline has been formed in the pores of Cu- or Fe-exchanged MCM-41 by adsorption of aniline vapour and subsequent oxidative polymerization (Figure 7.23), and these molecular wires demonstrate significant electronic conduction, although less than that of bulk polyaniline. Pyrolysis of polyacrylonitrile in the pores produces a graphitelike carbon chain, which exhibits microwave conductivity ten times that of bulk carbonized polyacrylonitrile. Such materials have potential for use in information processing as storage capacitors. 

Liljeroth et al. [80] used SECM in the feedback mode to study the electronic conductivity of a film of gold nanoparticles deposited at various pressures on a nonconductive substrate. They were able to observe an insulator-to-metal transition associated with a change in surface pressure. Unwin Whitworth et al. [83] have also developed a method to determine the electronic conductivity of ultrathin films using SECM under steady-state conditions. They obtained analytical approximations for the fitting of approach curves. The usefulness of their approach was demonstrated by investigating the effect of surface pressure on conductivity of a polyaniline monolayer at the water-air interface. 

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