Oxide cathodes redox potentials

In the case of CaCl2 and NaCl, the order corresponds with the corrosion behaviour expected from cathodic polarisation curves . The order of aggressiveness of chlorides can also be explained on the basis of redox potentials of the melts, calculated on thermodynamic grounds from the free energies of formation of the appropriate oxides and chlorides . The order of aggressiveness of nitrates is complicated by passivity effects , while that of alkalis in contact with air is... 

Corrosion or mixed potentials (a) Active corrosion in acid solutions (b) Passive metal in acid solutions Potential dependent on the redox potential of the solution and the kinetics of the anodic and cathodic reactions. Potential dependent on the kinetics of the h.e.r. on the bare metal surface. Potential is that of an oxide-hlmed metal, and is dependent on the redox potential of the solution. Zn in HCI Stainless steel in oxygenated H2SO4... 

In redox mediation, to have an effective electron exchange, the thermodynamic redox potentials of the enzyme and the mediator have to be accurately matched. For biocatalytic electrodes, efficient mediators must have redox potentials downhill from the redox potential of the enzyme a 50 mV difference is proposed to be optimal [1, 18]. The tuning of these potentials is a compromise between the need to have a high cell voltage and a high catalytic current. Furthermore, an obvious requirement is that the mediator must be stable in the reduced and oxidized states. Finally, for operation of a membraneless miniaturized biocatalytic fuel cell, the mediators for both the anode and the cathode must be immobilized to prevent power dissipation by solution redox reactions between them. 

If the potentials of the FDH-interfaced electrode are controlled to be more positive than the redox potential of PQQ (0.06 V), it is expected that the reduced form of FDH (FDH-PQQH2) will reoxidize to the active oxidized form (FDH-PQQ) by transferring two electrons to the electrode thus a continuous flow of anodic current is observed upon the addition of fructose. At a lower potential such as 0.1 V the background current was cathodic and magnitude was very high as the rest potential of the electrode is around 0.35 V. To make... 

Fig. 8-90. Normalized cathodic cur> rent of redox reactions of hydrated redox particles as a function of standard redox potential at n-type electrodes of zinc oxide / (n, cqx) = normalized cathodic reaction current n, = concentration of interfacial electrons Cqx = concentration of oxidant particles au = arbitrary unit. [From Morrison, 1969,1980.]...

Figure 8-30 shows the normalized cathodic transfer current of redox electrons for several redox reactions as a function of the standard redox potential sbdox on n- semiconductor electrodes of zinc oxide in aqueous solutions. The bell-like curve observed in Fig. 8-30 is in agreement with the forgoing conclusion that the maximum current occurs at the electrode potential at whidi tox equals e. ... 

In order to illustrate the application of LSV in mechanistic analysis we can look at the redox behavior of the formazan-tetrazolium salt system which we studied some years ago [17], 1,3,5-Triphenyl formazane was oxidized at controlled potential in CH3CN-Et4NC104 solution to 2,3,5-triphenyl tetrazolium perchlorate which was then isolated in quantitative yield. Coulometry showed that the overall electrode reaction was a two-electron oxidation. It has been shown that the rate of variation of Ep with log v was 30 mV per decade of sweep rate and that there was no variation of the peak potential with the concentration of 1,3,5-triphenylformazan. According to Saveant s diagnostic criteria (Table 1), four mechanistic schemes were possible e-C-e-p-p, e-C-d-p-p, e-c-P-e-p and e-c-P-d-p. If cyclization is the rate-determining step, then the resulting e-C-e-p-p and e-C-d-p-p mechanisms would not imply variation of Ep with the concentration of base. However, we have observed the 35 mV shift of Ep cathodically in the presence of 4-cyanopyridine as a b e. These observations ruled out the first two mechanisms. The remaining possibilities were then e-c-P-e and e-c-P-d, as shown in Scheme 3. 

The cathode materials employed for the early lithium-based systems were 3.0 V class oxides or sulfides thus, the redox potential for the additive should be located in the neighborhood of 3.2—3.5 V. Accordingly, the first generation redox additive proposed by Abraham et al. was based on the iodine/ iodide couple, which could be oxidatively activated at the cathode surface at 3.20 V and then reduced at the lithium surface. " " " 2° For most of the ether-based solvents such as THF or DME that were used at the time, the oxidation potential of iodide or triiodide occurred below that of their major decompositions, while the high diffusion coefficients of both iodine and iodide in these electrolyte systems ( 3 x 10 cm s ) offered rapid kinetics to shuttle the overcharge current. Similarly, bromides were also proposed.Flowever, this class of halide-based additives were deemed impractical due to the volatility and reactivity of their oxidized forms (halogen). 

A similar mechanism could operate in the reduction of oxygen on chelate catalysts, as in the organic cathodes with air regeneration described by Alt, Binder, Kohling and Sandstede 13-40>. These cathodes contain a reversible insoluble quinone/hydroquinone system. The quinone, which is electrochemically reducible, can be obtained either by electrochemical oxidation or by purely chemical oxidation with H2O2 or oxygen (air). A cathodic current is observed in these systems only at potentials below the redox potential, and unusually hard current/ voltage characteristic curves are obtained. 

The counterpart of anodically electrocatalyzed oxidation by redox oxides, namely the cathodic reduction of organic substrates by surface-coup led redox system with sufficiently negative redox potential, is almost unknown. Beck reports that specially prepared TiO coating on Ti-electrodes can be reduced cathodically and that the electrogenerated Ti(III) and Ti(II) species do in fact reduce nitrobenzene to aniline (207). 

As described above the oxidation potential of the platinum(III) species should be equal or more negative than —0.28 V. This is supported by the pH dependence of 4-CP photodegradation in presence of 4.0% H2[PtCl6]/TH (10). The reaction is slowed down in basic media and almost suppressed at pH = 11-12. Since Bahnemann et al. observed a contrary tendency, i.e., a slight increase in 4-CP degradation rate with increasing pH for unmodified P25 (42), our observation may be connected with a too cathodic position of the flatband potential and therefore the electron injection should be much slower in basic suspensions. This supports the estimation of the redox potential of Pt4+ 3+ couple to be at ca. —0.3 to —0.4 V, i.e., around the flatband potential of the catalyst at pH = 7-8. However,... 

In I/E curves the onset of photocurrent is expected from classical theories to occur near the Hatband potential as measured in the dark (Efb (d)), i.e. where the majority carrier current starts too. However, a large shift of the onset potential is seen especially if no additional redox couple is present in the aqueous electrolyte, in cathodic direction for p-, in anodic direction for n-type materials (Fig. 1). This shift depends on the light intensity but saturates already at relatively low intensities (Memming, 1987). If minority carrier acceptors (oxidants for p- and reductants for n-type semiconductors) are added to the solution, the onset can be shifted back to Efb (d) if they have the appropiate redox potential. In principal two types of redox couples can be found those which lead to a shift of the photocurrent onset potential and those which don t. The transition between the two classes occurs at a specific redox potential. 

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