Redox-polymer modified electrodes characterization

Since the appearance of the redox [ii, iii] and conducting [iv] polymer-modified electrodes much effort has been made concerning the development and characterization of electrodes modified with electroactive polymeric materials, as well as their application in various fields such as -> sensors, actuators, ion exchangers, -> batteries, -> supercapacitors, -> photovoltaic devices, -> corrosion protection, -> electrocatalysis, -> elec-trochromic devices, electroluminescent devices (- electroluminescence) [i, v-viii]. See also -> electrochemically stimulated conformational relaxation (ESCR) model, and -> surface-modified electrodes. 

The electrochemistry of redox proteins is characterized by a strong dependence on the nature of the electrode surface. Extensive studies by Hill etal. (cited in Refs. 31-33) show that provided the electrode surface is modified to be compatible with the redox protein, direct electrochemistry can be rapid. Their studies have emphasized the importance of the orientation of the protein at the electrode surface so that the distance over which the electron must transfer is not excessive. This is important because redox sites in these proteins are generally located toward one side of the protein, and the exponential dependence of the electron transmission coefficient/ei on distance means that the rate of electron transfer drops rapidly as distance increases (Fig. 9.11). Most of this work has used low molecular weight modifiers adsorbed at the electrode surface, " although similar effects should be possible at polymer-modified electrode surfaces. 

Using preformed redox polymers as electrode modifiers has the advantage of completely characterizing polymers prior to modifying the electrode surface. Control of the layer thickness of the deposited films can be achieved by carefully controlling the amount deposited by using drop- or spin-coating procedures. 

We briefly mention here the use of the ferrocene/ferrocenium redox couple to mediate electron transfer on the oxidation (anodic) side, especially in derivatized electrode. This broad area has been reviewed [349]. For instance, polymers and dendrimers containing ferrocene units have been used to derivatize electrodes and mediate electron transfer between a substrate and the anode. Recently, ferrocene dendrimers up to a theoretical number of 243 ferrocene units were synthesized, reversibly oxidized, and shown to make stable derivatized electrodes. Thus, these polyferrocene dendrimers behave as molecular batteries (Scheme 42). These modified electrodes are characterized by the identical potential for the anodic and cathodic peak in cyclic voltammetry and by a linear relationship between the sweep rate and the intensity [134, 135]. Electrodes modified with ferrocene dendrimers were shown to be efficient mediators [357-359]. For the sake of convenience, the redox process of a smaller ferrocene dendrimer is represented below. 

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