Cyclic voltammetry electrode materials

Polythiophene films can be electrochemically cycled from the neutral to the conducting state with coulombic efficiencies in excess of 95% [443], with little evidence of decomposition of the material up to + 1.4 V vs. SCE in acetonitrile [37, 54, 56, 396,400] (the 3-methyl derivative being particularly stable [396]), but unlike polypyrrole, polythiophene can be both p- and n-doped, although the n-doped material has a lower maximum conductivity [444], Cyclic voltammetry shows two sets of peaks corresponding to the p- and n-doping reactions, with E° values at approximately + 1.1 V and — 1.4 V respectively (vs. an Ag+/Ag reference electrode)... 

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]. 

Whereas the work function of the electrodes is measured by photoelectron spectroscopy, the organic materials are usually characterized by cyclic voltammetry [226]. The values can be extrapolated to the gas phase by choosing an... 

For further contributions on the dia-stereoselectivity in electropinacolizations, see Ref. [286-295]. Reduction in DMF at a Fig cathode can lead to improved yield and selectivity upon addition of catalytic amounts of tetraalkylammonium salts to the electrolyte. On the basis of preparative scale electrolyses and cyclic voltammetry for that behavior, a mechanism is proposed that involves an initial reduction of the tetraalkylammonium cation with the participation of the electrode material to form a catalyst that favors le reduction routes [296, 297]. Stoichiometric amounts of ytterbium(II), generated by reduction of Yb(III), support the stereospecific coupling of 1,3-dibenzoylpropane to cis-cyclopentane-l,2-diol. However, Yb(III) remains bounded to the pinacol and cannot be released to act as a catalyst. This leads to a loss of stereoselectivity in the course of the reaction [298]. Also, with the addition of a Ce( IV)-complex the stereochemical course of the reduction can be altered [299]. In a weakly acidic solution, the meso/rac ratio in the EHD (electrohy-drodimerization) of acetophenone could be influenced by ultrasonication [300]. Besides phenyl ketone compounds, examples with other aromatic groups have also been published [294, 295, 301, 302]. 

Apart from the insulating polymeric matrices, conductive polymers such as polypyrrole and polyaniline have been used as nanocomposite electrodes by chemical or electrochemical polymerization [13, 17, 116, 117]. Such materials provide high conductivity and stability. However, the use of insulating polymers can be more advantageous than the conductive polymers when employed in cyclic voltammetry. 

Figure 51. Cathodic and anodic stability of LiBOB-based electrolytes on metal oxide cathode and graphitic anode materials Slow scan cyclic voltammetry of these electrode materials in LiBOB/EC/EMC electrolyte. The scan number and Coulombic efficiency (CE) for each scan are indicated in the graph. (Reproduced with permission from ref 155 (Eigure 2). Copyright 2002 The Electrochemical Society.)...

The ferrocenyl dendrimers were electrodeposited in their oxidized forms onto the electrode surfaces (platinum, glassy-caibon, and gold) either by controlled potential electrolysis or by repeated cycling between the appropriate anodic and cathodic potential limits therefore the amount of electroactive material electrode-posited can be controlled with the electrolysis time or the number of scans. The electrochemical behavior of films of the polyfeirocenyl dendrimers was studied by cyclic voltammetry in fresh CH2CI2 and CHjCN solutions containing only supporting electrolyte. 

Chapter 1 serves as an introduction to both volumes and is a survey of the fundamental principles of electrode kinetics. Chapter 2 deals with mass transport — how material gets to and from an electrode. Chapter 3 provides a review of linear sweep and cyclic voltammetry which constitutes an extensively used experimental technique in the field. Chapter 4 discusses a.c. and pulse methods which are a rich source of electrochemical information. Finally, Chapter 5 discusses the use of electrodes in which there is forced convection, the so-called hydrodynamic electrodes . 

Cyclic voltammetry can (i) determine the electrochemical reversibility of the primary oxidation (or reduction) step (ii) allow the formal potential, E°, of the reversible process to be estimated (iii) provide information on the number of electrons, n, involved in the primary process and (iv) allow the rate constant for the decomposition of the M"+ species to be measured. Additional information can often be obtained if intermediates or products derived from M"+ are themselves electroactive, since peaks associated with their formation may be apparent in the cyclic voltam-mogram. The idealized behaviour illustrated by Scheme 1 is a relatively simple process more complicated processes such as those which involve further electron transfer following the chemical step, pre-equilibria, adsorption of reactants or products on the electrode surface, or the attack of an electrogenerated product on the starting material, are also amenable to analysis. 

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