Polymer polyaniline

A thin layer deposited between the electrode and the charge transport material can be used to modify the injection process. Some of these arc (relatively poor) conductors and should be viewed as electrode materials in their own right, for example the polymers polyaniline (PAni) [81-83] and polyethylenedioxythiophene (PEDT or PEDOT) [83, 841 heavily doped with anions to be intrinsically conducting. They have work functions of approximately 5.0 cV [75] and therefore are used as anode materials, typically on top of 1TO, which is present to provide lateral conductivity. Thin layers of transition metal oxide on ITO have also been shown [74J to have better injection properties than ITO itself. Again these materials (oxides of ruthenium, molybdenum or vanadium) have high work functions, but because of their low conductivity cannot be used alone as the electrode. 

The monomer of the conducting polymer polyaniline is the compound aniline (aminobenzene). (a) Draw the structural formula of the aniline monomer. What is the hybridization of the N atom in (b) aniline (c) polyaniline (d) Indicate the locations of lone pairs, if any, in polyaniline, (e) Do the N atoms help to carry the current Explain your reasoning. See Box 19.1. 

Oxidoreductases Transferases Hydrolases Lyases Isomerases Ligases Phenolic polymers, polyanilines, vinyl polymers Polysaccharides, cyclic oligosaccharides, polyesters Polysaccharides, polyesters, polycarbonates, poly(amino acid)s, polyphosphates... 

Numerous workers126-132 have combined PB with the conducting polymer polyaniline in complementary ECDs that exhibit deep blue-to-light green electrochromism. Electrochromic compatibility is obtained by combining the colored oxidized state of the polymer1 with the blue PB, and the bleached reduced state of the polymer with PG (Equation (17)) ... 

Conducting polymers, polyaniline, catalytic activity, PANI/expanded graphite composites, metal-air batteries, primary rechargeable cells. 

The use of conjugated polymer as membranes to separate various liquid mixtures has been reported in the literature [19,20], From those, polyaniline (PANi) is one of the most interesting and studied conjugated polymers. Polyaniline is usually prepared by direct oxidative polymerization of aniline in the presence of a chemical oxidant, or by electrochemical polymerization on different electrode materials [21,22], The possible interconversions between different oxidation states and protonated and depronated states [23], figure 4, make this material remarkable for different purposes. Under most conditions, PANi... 

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... 

A recent example of the application of in situ FTIR reflectance spectroscopy to modified electrodes can be found in the work of Korzeniewski and her group [54] on Pt electrodes coated with films of the polymer polyaniline. Figure 13.6 shows the reflectance spectrum (in AR/R units) of a polyaniline film-coated electrode as a function of applied potential. As the film becomes more oxidized, the band at 1320 cm-1 is shifted to higher energies, a result consistent with an increasing C-N bond strength upon oxidation [54]. The interac-... 

As a conducting polymer, polyaniline has many electronics-related applications, such as rechargeable batteries (Tsutsumi et al. 1995), multilayer heterostructure light-emitting diode devices (Onoda Yoshino 1995), biosensors (Bartlett Whitaker 1987), elec-trochromic windows (Nguyen Dao 1989), and nonlinear optical materials (Papacostadi-nou Theophilou 1991). Polyaniline may be prepared from aniline by both electrochemi-... 

The signal travels through a thick, or even molecularly thin, semiconductor that connects these electrodes it could be an inorganic semiconductor (doped Si, doped Ge), an organic conducting polymer (polyaniline, polythiophene, polyacetylene), a carbon nanotube, or an organic semiconductor (sexithiophene). 

The formation of -aminodiphenylamine is supposed to be the key intermediate in the formation of a dark green precipitate at the electrode surface during continued electrolysis of acidic aniline solutions. This has been characterized as an oligomer of aniline, for example, as the octamer emeraldine formed by a cascade of head-to-tail condensations [38,39]. Nelson, however, explained it as a mixture of mainly quinhydrone with a small amount of benzidine salt [37]. Today the electropolymerization of aniline under strongly acidic conditions is intensively studied as an important way to form the conducting polymer polyaniline [40] (see Chapters 31 and 32). 

Different electron-conducting polymers (polyaniline, polypyrrole, polythiophene) are considered as convenient substrates for the electrodeposition of highly dispersed metal electrocatalysts. The preparation and the characterization of electronconducting polymers modified by noble metal nanoparticles are first discussed. Then, their catalytic activities are presented for many important electrochemical reactions related to fuel cells oxygen reduction, hydrogen oxidation, oxidation of Cl molecules (formic acid, formaldehyde, methanol, carbon monoxide), and electrooxidation of alcohols and polyols. 

Fig. 13.8 An example of screen-shot for analysis of absolute (up) and relative (down) sensitivity vs. polymer thickness. The values are normalized to the relative sensitivity of pure polyaniline (ANI). Polymer polyaniline. Polymer thickness was varied as the polymerization charge, the value in abscissa corresponds the charge in coulombs, the electrode size 400 x 400pm. Analyte 3.5ppm HC1. Reprinted from30 with permission (copyright 2008 American Chemical Society)...

In addition to catalysis of small molecule transformations and biocatalysis, non-functionalized LLC phases used as reaction media have also been found to accelerate polymerization reactions as well. For example, the L and Hi phases of the sodium dodecylsulfate/n-pentanol/sulfuric acid system have been found to lower the electric potential needed to electropolymerize aniline to form the conducting polymer, polyaniline [110]. In this system, it was also found that the catalytic efficiency of the L phase was superior to that of the Hi phase. In addition to this work, the Ii, Hi, Qi, and L phases of non-charged Brij surfactants (i.e., oligo(ethylene oxide)-alkyl ether surfactants) have been observed to accelerate the rate of photo-initiated radical polymerization of acrylate monomers dissolved in the hydrophobic domains [111, 112]. The extent of polymerization rate acceleration was found to depend on the geometry of the LLC phase in these systems. Collectively, this body of work on catalysis with non-functionalized LLC phases indicates that LLC phase geometry and system composition have a large influence on reaction rate. 

This diol was mixed with other diols, then reacted with diisocyanates to form polyurethanes. The electrically conducting polymers, polyaniline and polypyrrole, prevent corrosion of steel.105 One of the best formulations uses polyaniline with zinc nitrate, which is then covered with an epoxy resin topcoat. Polyorganosiloxanes have been grafted to starch using the sol-gel method with alkoxysi-lanes. These materials have been complexed with cerium ions to provide corrosion protection for aircraft that is expected to be 50% cheaper than conventional coatings.106... 

As an environmentally stable conducting polymer, polyaniline has been recognized as a potential candidate for application in secondary battery electrodes, sensors, electrochromic display devices, microelectronics, ion-exchange resins etc. [151-161]. 

For molybdenum and arsenic oxides [1—3], it has been shown that the modification of the oxide surface by adsorption of a conducting polymer (polyaniline, in these cases) can exert remarkable effects on the electrochemical properties of the oxides. 

By the mid-80s it was clear to most researchers that success on the conductivity side had taken its toll on polymer processability. Attention turned back to restoring the solubility and mechanical properties of the polymer. Polyaniline received the most attention initially. The nonconductive emeraldine base form is soluble in A-methylpyrrolidone [28] and films can be cast. Subsequent doping with a protonic acid from aqueous solution, or in situ with a photo-acid generator [45], is necessary to achieve conductivity. Polyaniline is also soluble in sulfuric acid, not the most convenient of solvents. Nevertheless it proved possible to spin fibers [46], cast films and extmde sheets of conductive polyaniline sulfate, but the laboratory experiments did not make the transition into large-scale manufacmring. 

T.V. Shishkanova, P. Matejka, V. Krai, I. Sedenkova, M. Trchova, and J. Stejskal Optimization of the thickness of a conducting polymer, polyaniline, deposited on the surface of poly(vinyl chloride) membranes A new way to improve their potentiometric response. Anal. Chim. Acta, 624, 238-246 (2008). 

The book starts with an introductory chapter about conductive polymers. For those who are familiar with nanotechnology, this chapter is a guiding star and for polymer scientists, it is a reminder that from where we have started. The two next chapters are typical ones to introduce the realms of nanostructured conductive polymers. Polyaniline is considered as a prototype and among most popular conductive polymers. Chapter 3 discusses some interesting features in surface studies of conductive polymer, while surface analysis is always a key concept in the realm of nanotechnology. 

Henry Letheby, a lecturer in chemistry and toxicology at the College of London Hospital, obtained a partially conducting material in 1862 by the anodic oxidation of aniline in sulfuric acid. The material Letheby synthesized was a form of polyaniline. In the 1980s, the New Zealander Alan MacDiarmid of the University of Pennsylvania reinvestigated polyaniline, which is now a widely used conducting polymer. Polyaniline exists in a variety of oxidation states (Figure 27.12), each with different... 

---