Conducting polymers electrochemical model

Bieniasz LK (2001) Use of dynamically adaptive grid techniques for the solution of electrochemical kinetic equations. Patch-adaptive simulation of moving fronts in non-linear diffusion models of the switching of conductive polymers. Electrochem Commim 3 149-153... 

Most of the usual conducting polymers have a cross-linked stmcture (Fig. 3), but again they can be electrochemically oxidized and reduced. The electrochemical responses must follow electrochemical models and... 

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. 

Later we will describe both oxidation and reduction processes that are in agreement with the electrochemically stimulated conformational relaxation (ESCR) model presented at the end of the chapter. In a neutral state, most of the conducting polymers are an amorphous cross-linked network (Fig. 3). The linear chains between cross-linking points have strong van der Waals intrachain and interchain interactions, giving a compact solid [Fig. 14(a)]. By oxidation of the neutral chains, electrons are extracted from the chains. At the polymer/solution interface, positive radical cations (polarons) accumulate along the polymeric chains. The same density of counter-ions accumulates on the solution side. 

Most of the models developed to describe the electrochemical behavior of the conducting polymers attempt an approach through porous structure, percolation thresholds between oxidized and reduced regions, and changes of phases, including nucleation processes, etc. (see Refs. 93, 94, 176, 177, and references therein). Most of them have been successful in describing some specific behavior of the system, but they fail when the... 

Our laboratory has planned the theoretical approach to those systems and their technological applications from the point of view that as electrochemical systems they have to follow electrochemical theories, but as polymeric materials they have to respond to the models of polymer science. The solution has been to integrate electrochemistry and polymer science.178 This task required the inclusion of the electrode structure inside electrochemical models. Apparently the task would be easier if regular and crystallographic structures were involved, but most of the electrogenerated conducting polymers have an amorphous and cross-linked structure. 

Equations (37) and (38), along with Eqs. (29) and (30), define the electrochemical oxidation process of a conducting polymer film controlled by conformational relaxation and diffusion processes in the polymeric structure. It must be remarked that if the initial potential is more anodic than Es, then the term depending on the cathodic overpotential vanishes and the oxidation process becomes only diffusion controlled. So the most usual oxidation processes studied in conducting polymers, which are controlled by diffusion of counter-ions in the polymer, can be considered as a particular case of a more general model of oxidation under conformational relaxation control. The addition of relaxation and diffusion components provides a complete description of the shapes of chronocoulograms and chronoamperograms in any experimental condition ... 

Figure 14. Chronoampcrometry of polypyirole in acetonitrile containing 0.1M Li004. Potential steps were from the potential indicated to +200 mV.163 (Reprinted from T. F. Otero, H. Grande, and J. Rodriguez, An electromechanical model for the electrochemical oxidation of conducting polymers, Synth. Met. 76(1-3), 293-293, 1996, with kind permission from Elsevier Sciences S.A.)...

Chain length is another factor closely related to the structural characterization of conducting polymers. The importance of this parameter lies in its considerable influence on the electric as well as the electrochemical properties of conducting polymers. However, the molecular weight techniques normally used in polymer chemistry cannot be employed on account of the extreme insolubility of the materials. A comparison between spectroscopic findings (XPS, UPS, EES) for PPy and model calculations has led some researchers to conclude that 10 is the minimum number of monomeric units in a PPy chain, with the maximum within one order of magnitude n9- 27,i28) mechanical qualities of the electropolymerized films,... 

Electrochemically stimulated conformational relaxation model (ESCR model) — This model [i, ii] describes the relaxation phenomena occurring during the charging and discharging of -> conducting polymers. It assumes that applying an anodic -> overpotential to a neutral conjugated polymer, as a first step, an expansion of the closed polymeric structure occurs. In this way, partial oxidation takes place and counter ions from the solution enter the solid polymer under the influence of an electrical field at those points of the polymer/electrolyte... 

Hwang B. J., Yang J. Y., and Lin C. W., A Microscopic Gas-sensing model for Ethanol sensors based on conductive polymer composite from polypyrrole and poly(ethylene oxide), J. Electrochem. Soc. 146, 1231-1236, 1999. 

Voltammetric sensors based on chemically modified electrodes (conducting polymers, phthalocyanine complexes) with improved cross-selectivity were developed for the discrimination of bitter solutions [50], The performance and capability were tested by using model solutions of bitterness such as magnesium chloride, quinine, and four phenolic compounds responsible for bitterness in olive oils. The sensors gave electrochemical responses when exposed to the solutions. A multichannel taste sensor was constructed using the sensors with the best stabilities and cross-selectivities and PCA of the signals allowed distinct discrimination of the solutions. 

M.R. Warren and J.D. Madden, Electrochemical switching of conducting polymers A variable resistance transmission line model, J. Electroanal. Chem., 590 (1), 76-81 (2006). 

Xiao et al. investigated the electrochemical synthetic mechanism of conducting-polymer nanotubes in a porous alumina template using poly(3,4-ethylenedioxythiophaie) (PEDOT) as a model compound [70]. The electrochemical polymerization of EDOT was performed potentiostatically at various potentials from 1.0 to 1.8 V (vs. Ag/AgCl) in a solution containing EDOT, LiC104, and acetonitrile. They found that the tubular portion of the nanotube structure increased as the applied potential increased from 1.4 to 1.8 V at a fixed concentration of EDOT, while the tubular portion decreased with increasing monomer concentration from 10 to 100 mM at a fixed poteitial of 1.6 V. 

When used in different kinds of electrochemical equipment the membranes are in contact with aqueous solutions of the low molecular weight electrolytes in which they swell. Moreover, a certain amount of the ambient solution penetrates the voids or pores in the membrane. So the swollen membrane is a multiphase system composed of an ion containing component appearing in a gel state, an inert partly crystalline polymer, and the electrolyte filling any voids or nonselec-tive domains, all of them in varying amounts. For such a system it is possible to calculate the approximate phase composition based on the conductivity and the multilayer electrochemical model. We presented such a model at the First Italian-Polish Seminar on Multi-component Polymeric Systems in 1979. 

An alternative model uses the Crank-Nicholson method to generate a voltammogram that consists of a layer with a series of microscopic formal potentials, most situated at O.OV and the rest equally spaced 50 mV apart. This also yields a voltanmiogram (Fig. 6.16) similar to the experimental one (Fig. 6.14). The basis for this is the fact that different oligomers of different chain length possess a range of redox potentials. Thus at least qualitatively, two models may account for the electrochemical behavior of a conducting polymer coated on an electrode. 

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