Conductive polymers electrochemical synthesis

Sherman, B. C., W. B. Euler, and R. R. Force. 1994. Polyaniline—A conducting polymer electrochemical synthesis and electrochromic properties. Journal of Chemical Education 71 (4) A94-A95. 

In 1862, Letheby [30] discussed the production of a blue substance by the electrolysis of sulfate of aniline, nowadays considered as the first reported electrochemical synthesis of a conjugated polymer, in his case poly(aniline). Since then a great number of different monomers were synthesized that form conducting polymers. The synthesis method of choice for preparing these polymers involves the anodic oxidation of a suitable monomer M into a cation radical... 

Polypyrrole and many of its derivatives can be synthesized via simple chemical or electrochemical methods [120]. Photochemically initiated and enzyme-catalyzed polymerization routes have also been described but less developed. Different synthesis routes produce polypyrrole with different forms chemical oxidations generally produce powders, while electrochemical synthesis leads to films deposited on the working electrode and enzymatic polymerization gives aqueous dispersions [Liu. Y. C, 2002, Tadros. T. H, 2005 and Wallace. G. G, 2003]. As mentioned above the electrochemical polymerization method is utilized extensively for production of electro active/conductive films. The film properties can be easily controlled by simply varying the electrolysis conditions such as electrode potential, current density, solvent, and electrolyte. It also enables control of thickness of the polymers. Electrochemical synthesis of polymers is a complex process and various factors such as the nature and concentration of monomer/electrolyte, cell conditions, the solvent, electrode, applied potential and temperature, pH affects the yield and the quality of the film... 

Here we introduce a personal point of view about the interactions between conducting polymers and electrochemistry their synthesis, electrochemical properties, and electrochemical applications. Conducting polymers are new materials that were developed in the late 1970s as intrinsically electronic conductors at the molecular level. Ideal monodimensional chains of poly acetylene, polypyrrole, polythiophene, etc. can be seen in Fig. 1. One of the most fascinating aspects of these polymeric... 

Empirical kinetics are useful if they allow us to develop chemical models of interfacial reactions from which we can design experimental conditions of synthesis to obtain thick films of conducting polymers having properties tailored for specific applications. Even when those properties are electrochemical, the coated electrode has to be extracted from the solution of synthesis, rinsed, and then immersed in a new solution in which the electrochemical properties are studied. So only the polymer attached to the electrode after it is rinsed is useful for applications. Only this polymer has to be considered as the final product of the electrochemical reaction of synthesis from the point of view of polymeric applications. 

The synthesis of thin films of organic conducting polymers on a nanometer scale is one of the challenges of nanotechnology. Electrochemical poly-... 

Chemical and electrochemical techniques have been applied for the dimensionally controlled fabrication of a wide variety of materials, such as metals, semiconductors, and conductive polymers, within glass, oxide, and polymer matrices (e.g., [135-137]). Topologically complex structures like zeolites have been used also as 3D matrices [138, 139]. Quantum dots/wires of metals and semiconductors can be grown electrochemically in matrices bound on an electrode surface or being modified electrodes themselves. In these processes, the chemical stability of the template in the working environment, its electronic properties, the uniformity and minimal diameter of the pores, and the pore density are critical factors. Typical templates used in electrochemical synthesis are as follows ... 

The synthesis of conducting polymers can be divided into two broad areas, these being electrochemical and chemical (i.e., non-electrochemical). Whilst the latter may be considered to be outside the scope of this review, it is worth noting that many materials which are now routinely synthesised electrochemically were originally produced via non-electrochemical routes, and that whilst some may be synthesised by a variety of methods many, most notably polyacetylene, are still only accessible via chemical synthesis. In view of this it is useful to have an appreciation of the synthesis of these materials via routes which do not involve electrochemistry. 

This volume combines chapters oriented towards new materials with chapters on experimental progress in the study of electrochemical processes. G. E Evans reviews the electrochemical properties of conducting polymers, materials which are most interesting from a theoretical point of view and promise to open up new fields of application. His approach gives a survey of the main classes of such polymers, describing their synthesis, structure, electronic and electrochemical properties and, briefly, their use as electrodes. 

In this article we report the synthesis and electrochemical properties of the polymer derived from oxidation of X, poly(I), and the characteristics of a microelectrochemical transistor based on the polymer. Poly(I), which is formed by electrochemical oxidation of X, Equation 1, consists of a conducting polymer backbone, polythiophene. 

Much work has been directed towards the synthesis of thiophene oligomers and polymers. This is due to the current interest in research on conducting polymers and molecular electronics (92CRV711). Two main approaches have been used for making such polymers (i) chemical (e.g. FeCl3) or electrochemical oxidation of monomeric thiophenes and (ii) transition metal-catalyzed cross-coupling reactions. 

Useful electrochemical synthesis of conducting polymers requires a combination of conductivity with insolubility in the electrolyte, which causes the polymer to precipitate, hopefully directly on the electrode surface, as a coherent film which does not passivate the electrode and may be removable from its surface for further study. Electrochemical synthesis is generally limited to rather small amounts of polymer, although a method of producing large amounts of film by continuous stripping of a rotating electrode has been described 109). 

These polymerizations depend upon the ability to oxidize the monomer to a radical cation, whose further reactions lead to polymer. Since the oxidation potentials of the polymers are lower than those of the corresponding monomer, the polymer is simultaneously oxidized into a conducting state so that it is non-passivating. Some of the more important electrochemically-synthesised structures are discussed in more detail below and Chandler and Pletcher U4) have reviewed the electrochemical synthesis of conducting polymers. Detailed discussion in terms of thermodynamic parameters is impossible because the polymerizations are irreversible, so that E0 is undefined for the monomer-polymer equilibrium. 

PolyQj-Phenylene) is probably the most thermally and oxidatively stable conducting polymer known and has been of interest to polymer scientists both for its conducting properties and for its stability. Its synthesis by step-reaction polymerization or by chemical or electrochemical oxidation invariably gives powders or rather poor quality films, so that a precursor route would be very attractive. 

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