Electrode-Modified Materials

A significant part of solid state electrochemistry is concentrated in the attachment of solid materials to the surface of a basal, inert electrode. This process will, in the following, be termed electrode modification. 

The following methods have been proposed for electrode modification with porous materials. 

Coelectrodeposition with conducting polymers from a material-monomer slurry submitted to electropolymerization conditions. Thus, Rolison (1990) prepared uniform particle-polymer coatings from a drop of zeolite suspension in a pyrrole solution in Et4NC104/MeCN (see also Bessel and Rolison, 1997a). 

---

Mani, V., B. Devadas, and S.-M. Chen, Direct electrochemistry of glucose oxidase at electrochemically reduced graphene oxide-multiwalled carbon nanotubes hybrid material modified electrode for glucose biosensor. Biosensors and Bioelectronics, 2012. 41 p. 309-315. 

Obtaining information on the composition, structure, etc., of solid materials using voltammetric and related techniques can be performed by (1) recording the response of the material attached to an inert electrode and immersed into a suitable electrolyte or (2) recording the modification of the response of an electroactive probe in the electrolyte solution in contact with the material-modified electrode. In addition, the electrochemical response of such systems under the application of optical or magnetic inputs can also be used. 

The electrochemistry of conducting polymers has been the subject of several reviews2-8 and has been included in articles on chemically modified electrodes.9-14 The primary purpose of this chapter is to review fundamental aspects of the electrochemistry of conducting polymer films. Applications, the diversity of materials available, and synthetic methods are not covered in any detail. No attempt has been made at a comprehensive coverage of the relevant literature and the materials that have been studied. Specific examples have been selected to illustrate general principles, and so it can often be assumed that other materials will behave similarly. 

It was also observed that, with the exception of polyacetylene, all important conducting polymers can be electrochemically produced by anodic oxidation moreover, in contrast to chemical methoconducting films are formed directly on the electrode. This stimulated research teams in the field of electrochemistry to study the electrosynthesis of these materials. Most recently, new fields of application, ranging from anti-corrosives through modified electrodes to microelectronic devices, have aroused electrochemists interest in this class of compounds... 

The historical development of chemically electrodes is briefly outlined. Following recent trends, the manufacturing of modified electrodes is reviewed with emphasis on the more recent methods of electrochemical polymerization and on new ion exchanging materials. Surface derivatized electrodes are not treated in detail. The catalysis of electrochemical reactions is treated from the view of theory and of practical application. Promising experimental results are given in detail. Finally, recent advances of chemically modified electrodes in sensor techniques and in the construction of molecular electronics are given. 

The first reported electroorganic synthesis of a sizeable amount of material at a modified electrode, in 1982, was the reduction of 1,2-dihaloalkanes at p-nitrostyrene coated platinum electrodes to give alkenes. The preparation of stilbene was conducted on a 20 pmol scale with reported turnover numbers approaching 1 x 10. The idea of mediated electrochemistry has more frequently been pursued for inorganic electrode reactions, notably the reduction of oxygen which is of eminent importance for fuel cell cathodes Almost 20 contributions on oxygen reduction at modified... 

The field of modified electrodes spans a wide area of novel and promising research. The work dted in this article covers fundamental experimental aspects of electrochemistry such as the rate of electron transfer reactions and charge propagation within threedimensional arrays of redox centers and the distances over which electrons can be transferred in outer sphere redox reactions. Questions of polymer chemistry such as the study of permeability of membranes and the diffusion of ions and neutrals in solvent swollen polymers are accessible by new experimental techniques. There is hope of new solutions of macroscopic as well as microscopic electrochemical phenomena the selective and kinetically facile production of substances at square meters of modified electrodes and the detection of trace levels of substances in wastes or in biological material. Technical applications of electronic devices based on molecular chemistry, even those that mimic biological systems of impulse transmission appear feasible and the construction of organic polymer batteries and color displays is close to industrial use. 

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 use of non-inert and chemically modified electrodes and other strategies for the detection of species that are difficult to analyze with the normal electrode materials have been reviewed.55 Photosensitization prior to amperometric detection is another tactic that has proved useful for the analysis of substances that are normally considered to be electrochemically inert.56 The use of pulsed amperometry has recently been reviewed.57... 

Clearly this approach is not suitable for preparing large quantities of products, its main purpose being to permit the greatest amount of information to be obtained concerning the reactivity of a new material. If the coreactant is expensive and/or difficult to prepare then this procedure is invaluable. However, it is important to consider that the quantities of derivatized polymer obtained in this approach [ 10-6 mole based on -N=C repeat unit] might well represent sufficient material if such a process were to be used for the direct preparation of chemically modified electrodes (12), or incorporated into a planar microfabrication process, with which it would appear to be compatible. 

The new edition of Principles of Electrochemistry has been considerably extended by a number of new sections, particularly dealing with electrochemical material science (ion and electron conducting polymers, chemically modified electrodes), photoelectrochemistry, stochastic processes, new aspects of ion transfer across biological membranes, biosensors, etc. In view of this extension of the book we asked Dr Ladislav Kavan (the author of the section on non-electrochemical methods in the first edition) to contribute as a co-author discussing many of these topics. On the other hand it has been necessary to become less concerned with some of the classical topics the details of which are of limited importance for the reader. 

Most recently, they have developed" a cell configuration for the study of modified electrodes that employs, as a working electrode, colloidal graphite deposited onto kapton tape (typically employed as a window material). Such an arrangement minimizes attenuation due to the electrolyte solution. 

Modified electrodes containing cyclam derivatives have been prepared. The approach utilizing cyclam incorporated in Nafion film on a carbon electrode shows that the catalytic efficiency of the system is much lower than observed when the catalyst is adsorbed on the mercury. With electrodes prepared following the Langmuir Blodgett technique, only the electrode materials that allow the orientation of the monolayer so that the tail points to the substrate were found to be electrocatalytically active.165... 

CNTs have been one of the most actively studied electrode materials in the past few years due to their unique electronic and mechanical properties. From a chemistry point of view, CNTs are expected to exhibit inherent electrochemical properties similar to other carbon electrodes widely used in various electrochemical applications. Unlike other carbon-based nanomaterials such as C60 and C70 [31], CNTs show very different electrochemical properties. The subtle electronic properties suggest that carbon nanotubes will have the ability to mediate electron transfer reactions with electroactive species in solution when used as the electrode material. Up to now, carbon nanotube-based electrodes have been widely used in electrochemical sensing [32-35], CNT-modified electrodes show many advantages which are described in the following paragraphs. 

The first CNT-modified electrode was reported by Britto et al. in 1996 to study the oxidation of dopamine [16]. The CNT-composite electrode was constructed with bro-moform as the binder. The cyclic voltammetry showed a high degree of reversibility in the redox reaction of dopamine (see Fig. 15.3). Valentini and Rubianes have reported another type of CNT paste electrode by mixing CNTs with mineral oil. This kind of electrode shows excellent electrocatalytic activity toward many materials such as dopamine, ascorbic acid, uric acid, 3,4-dihydroxyphenylacetic acid [39], hydrogen peroxide, and NADH [7], Wang and Musameh have fabricated the CNT/Teflon composite electrodes with attractive electrochemical performance, based on the dispersion of CNTs within a Teflon binder. It has been demonstrated that the electrocatalytic properties of CNTs are not impaired by their association with the Teflon binder [15]. 

A way to circumvent the first problem is to ensure that all of the active material is present at the electrode surface. That is, employ a chemically modified electrode where a precursor to the active electrocatalyst is incorporated. The field of chemically modified electrodes Q) is approaching a more mature state and there are now numerous methodologies for the incorporation of materials that exhibit electrocatalytic activity. Furthermore, some of these synthetic procedures allow for the precise control of the coverage so that electrodes modified with a few monolayers of redox active material can be reproducibly prepared. Q)... 

---