Electrode polymer modified electrodes

The electrochemistry of a polymer-modified electrode is determined by a combination of thermodynamics and the kinetics of charge-transfer and transport processes. Thermodynamic aspects are highlighted by cyclic voltammetry, while kinetic aspects are best studied by other methods. These methods will be introduced here, with the emphasis on how they are used to measure the rates of electron and ion transport in conducting polymer films. Charge transport in electroactive films in general has recently been reviewed elsewhere.9,11... 

There has therefore been much interest in the mediation of redox reactions in solution by conducting polymer-modified electrodes. 

Intensive research on the electrocatalytic properties of polymer-modified electrodes has been going on for many years Until recently, most known coatings were redox polymers. Combining redox polymers with conducting polymers should, in principle, further improve the electrocatalytic activity of such systems, as the conducting polymers are, in addition, electron carriers and reservoirs. One possibility of intercalating electroactive redox centres in the conducting polymer is to incorporate redoxactive anions — which act as dopants — into the polymer. Most research has been done on PPy, doped with inter alia Co 96) RyQ- 297) (--q. and Fe-phthalocyanines 298,299) Co-porphyrines Evidently, in these... 

Fig. 3. Steady state concentration profiles of catalyst and substrate species in the film and diffusion layer for for various cases of redox catalysis at polymer-modified electrodes. Explanation of layers see bottom case (S + E) f film d diffusion layer b bulk solution i, limiting current at the rotating disk electrode other symbols have the same meaning as in Fig. 2 (from ref.

A.R. Hillman, in Reactions and Applications of Polymer Modified Electrodes, Electrochemical Science and Technology of Polymers (R.G. Linford, ed.), Elsevier, London (1987), p. 241. 

A discussion of the charge transfer reaction on the polymer-modified electrode should consider not only the interaction of the mediator with the electrode and a solution species (as with chemically modified electrodes), but also the transport processes across the film. Let us assume that a solution species S reacts with the mediator Red/Ox couple as depicted in Fig. 5.32. Besides the simple charge transfer reaction with the mediator at the interface film/solution, we have also to include diffusion of species S in the polymer film (the diffusion coefficient DSp, which is usually much lower than in solution), and also charge propagation via immobilized redox centres in the film. This can formally be described by a diffusion coefficient Dp which is dependent on the concentration of the redox sites and their mutual distance (cf. Eq. (2.6.33). 

Electrocatalytic regeneration of NADH has also been performed at polymer-modified electrodes with pendent [(r/s-Cs M cs) R h( bpy )C1]1 55,56 and [Rh(terpy)2]3+ 57 complexes, and coupled to enzymatic reduction with alcohol dehydrogenase.55,57... 

Mortimer, R. J. Dynamic processes in polymer modified electrodes. In Research in Chemical Kinetics, Compton, R. G., Hancock G., Eds. Elsevier Amsterdam, 1994 Vol. 2, pp 261-311. 

Yoon el al. [112] reported an all-solid-state sensor for blood analysis. The sensor consists of a set of ion-selective membranes for the measurement of H+, K+, Na+, Ca2+, and Cl. The metal electrodes were patterned on a ceramic substrate and covered with a layer of solvent-processible polyurethane (PU) membrane. However, the pH measurement was reported to suffer severe unstable drift due to the permeation of water vapor and carbon dioxide through the membrane to the membrane-electrode interface. For conducting polymer-modified electrodes, the adhesion of conducting polymer to the membrane has been improved by introducing an adhesion layer. For example, polypyrrole (PPy) to membrane adhesion is improved by using an adhesion layer, such as Nafion [60] or a composite of PPy and Nafion [117],... 

The information obtained from the previously described studies may be used to establish guideposts for the rational design and synthesis of electrochemical interfaces (in particular, of polymer modified electrodes) with high catalytic activity. 

Repeated scanning results in a continuous increase in the size of the wave at 0.6 V vs. Ag+/Ag, which is believed to be the oxidation wave of the polythiophene backbone of poly(I). The amount of polymer produced per unit of charge in the deposition has not been measured, but is qualitatively similar to polythiophene itself. A film of poly(I) on the Pt electrode can be seen with the naked eye. After deposition of poly(I), the polymer-modified electrode is transferred, after thorough rinsing, to clean electrolyte for further characterization. 

In the last 30 years considerable progress has been made in the development of tailor-made electrode surfaces by chemical modification [4-12] of electrodes surfaces with electroactive polymer films. A comprehensive description of electroactive polymer-modified electrodes can be found in the book edited by M. Lyons [13]. 

Manipulation of the Donnan potential in random polymer-modified electrodes can also be achieved. In the case of cast redox polyelectrolyte-modified electrodes one can control ion permselectivity by mixing the redox polymer with an oppositely charged polyelectrolyte in an appropriate ratio before film casting [123]. The same strategy can be followed in electropolymerized films by mixing the electroactive monomer with one of opposite charge [124]. 

During continuous redox cycling, the first cycle usually differs from the following ones. This effect is referred as break-in. In poly(vinylferrocene), PVF, films this has been related to the incorporation of solvent and ions into the film, decreasing its resistivity [132]. This effect has been observed for several polyelectrolyte and polymer-modified electrodes, for example, polyaniline [155]. 

Electrodes obtained by coating Nafion and cellulose acetate on electrode surface or the combination of Nafion/NO selective membranes and nonconducting polymer-modified electrode. 

Low-valent rhenium complexes are effective in the catalytic reduction of carbon dioxide. The conversion can be accomplished photolytically or electrochemically and is of interest with regard to fuel production and greenhouse gas remediation [9]. Electrocatalytic reduction of CO2 to CO is initiated by the reduction of fac-Re(bpy)(CO)3Cl or a related complex and can be accomplished in homogeneous solution [54, 55] or on a polymer-modified electrode surface [56]. Catalytic current... 

The surface of a carbon electrode was at first coated with a thin film of an anionic polymer such as sodium poly(styrene-sulfonate) 95) or nafion 96) (thickness thousand A) then the cationic Ru(bpy)2+ was adsorbed in the anionic layer electrostatically. The modification was also made by coating water insoluble polymer pendant Ru(bpy)2 + ( ) from its DMF solution 97). These Ru(bpy) +/polymer modified electrode gave a photoresponse in the MV2+ solution with the Pt counter electrode 95-97) The time-current behaviours induced by irradiation and cutoff of the light under argon are shown in Fig. 28. It is interesting to see that the direction of the photocurrent reversed at the electrode potential of ca. 0.4 V (vs. Ag—AgCl) under... 

Scanning tunneling (STM) was invented a decade ago by Binnig and Rohrer [72], and was first applied to the solid-liquid interface by Sonnenfeld and Hansma in 1986 [73]. Since then, there have been numerous applications of STM to in situ electrochemical experiments [74-76]. Because the STM method is based on tunneling currents between the surface and an extremely small probe tip, the sample must be reasonably conductive. Hence, STM is particularly suited to investigations of redox and conducting polymer-modified electrodes [76,77],... 

Having debated the mechanism of charge transport within the polymer film, it is now useful to consider a few examples of chemical applications of polymer modified electrodes. Electrodes coated with [Ru(bipy)2Cl(PVP)]Cl or [Ru(bipy)2(py)(PVP)]Cl2 show strong catalytic effects for the reduction of cerium(IV) and the oxidation of iron(II).52... 

Understanding of these fundamental reactions may help to design new functional materials such as nobel catalysts, compounds with biological activities, photo-conversion systems, semi-conducting or conducting materials, polymer modified electrodes, displays, sensors, and so on. 

Mediated electrocatalysis at a polymer-modified electrode charge and mass transport processes. 

Z. Li, H. Wang, S. Dong and E. Wang, Electrochemical investigation of DNA adsorbed on conducting polymer modified electrode, Anal. Sci., 13 (1997) 305-310. 

Theory of EHD Impedances for a Mediated Reaction on a Redox Polymer Modified Electrode [85]... 

The example considered is the redox polymer, [Os(bpy)2(PVP)ioCl]Cl, where PVP is poly(4-vinylpyridine) and 10 signifies the ratio of pyridine monomer units to metal centers. Figure 5.66 illustrates the structure of this metallopolymer. As discussed previously in Chapter 4, thin films of this material on electrode surfaces can be prepared by solvent evaporation or spin-coating. The voltammetric properties of the polymer-modified electrodes made by using this material are well-defined and are consistent with electrochemically reversible processes [90,91]. The redox properties of these polymers are based on the presence of the pendent redox-active groups, typically those associated with the Os(n/m) couple, since the polymer backbone is not redox-active. In sensing applications, the redox-active site, the osmium complex in this present example, acts as a mediator between a redox-active substrate in solution and the electrode. In this way, such redox-active layers can be used as electrocatalysts, thus giving them widespread use in biosensors. 

Polymer-modified electrodes have shown considerable utility as redox catalysts. In many cases, modified electrode surfaces show an improved electrochemical behavior towards redox species in solution, thus allowing them to be oxidized or reduced at less extreme potentials. In this manner, overpotentials can be eliminated and more selective determination of target molecules can be achieved. In this discussion, a mediated reduction process will be considered, although similar considerations can be used to discuss mediated oxidation processes. This mediation process between a surface-bound redox couple A/B and a solution-based species Y can be describes by the following ... 

However, the interplay between electrolyte and polymer layer needs to be considered when optimizing the performances of polymer-modified electrodes. Structural factors will influence the interfacial ion transport and this will have a direct effect on the mechanism and location within the polymer layer of the mediation process. The following discussion will show that the nature of the mediation process can be changed dramatically by changing the electrolyte, from a situation where an electrochemical sensor with good sensitivity is obtained, to a situation where the sensitivity obtained is not much better than that observed for the bare electrode. 

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