Redox reaction, regenerative

We suggest a predominantly kinetic explanation for these phenomena, involving the fine balance between the rate of the photocorrosion reaction on the one hand and that of the regenerative redox reactions on the other hand. 

The competition between redox reaction and anodic dissolution became very important in the development of stable regenerative solar cells on the basis of semiconductor-liquid junctions. As shown in the previous section, it is determined by the thermodynamic and kinetic properties of the processes involved. Information on the competitions between these reactions cannot be obtained entirely from current-potential curves, because in many cases they do not look very different upon addition of a redox system, especially if the current is controlled by the light intensity. Therefore, a rotating ring disc electrode (RRDE) assembly consisting of a semiconductor disc and a Pt ring is usually applied, i.e. a technique which makes it possible to determine separately the current corresponding to the oxidation of a redox system [62, 63]. 

The redox mechanism is also known as oxidation—reduction or regenerative mechanism of Rideal-Elay type. In this mechanism, a redox reaction takes place at the catalyst surface. More in detail, water oxidizes the catalyst surface and CO re-reduces the oxidized surface. Alternatively, a bifimctional way can be considered in which the CO adsorbed on the metal is oxidized by the support and the water fills the support oxygen vacancy (Ladebeck Kochloefl, 1995). If the symbol reported in the following expressions represents the active site, then this mechanism can be summarized as in the following reactions (1.5) and (1.6) ... 

The photovoltaic effect is initiated by light absorption in the electrode material. This is practically important only with semiconductor electrodes, where the photogenerated, excited electrons or holes may, under certain conditions, react with electrolyte redox systems. The photoredox reaction at the illuminated semiconductor thus drives the complementary (dark) reaction at the counterelectrode, which again may (but need not) regenerate the reactant consumed at the photoelectrode. The regenerative mode of operation is, according to the IUPAC recommendation, denoted as photovoltaic cell and the second one as photoelectrolytic cell . Alternative classification and terms will be discussed below. 

The electrochemical cell can again be of the regenerative or electrosynthetic type, as with the photogalvanic cells described above. In the regenerative photovoltaic cell, the electron donor (D) and acceptor (A) (see Fig. 5.62) are two redox forms of one reversible redox couple, e.g. Fe(CN)6-/4 , I2/I , Br2/Br , S2 /S2, etc. the cell reaction is cyclic (AG = 0, cf. Eq. (5.10.24) since =A and D = A ). On the other hand, in the electrosynthetic cell, the half-cell reactions are irreversible and the products (D+ and A ) accumulate in the electrolyte. The most carefully studied reaction of this type is photoelectrolysis of water (D+ = 02 and A = H2)- Other photoelectrosynthetic studies include the preparation of S2O8-, the reduction of C02 to formic acid, N2 to NH3, etc. 

In the presence of an oxidant, e.g., chlorate or bromate ions, the electrode reaction is transposed into an adsorption coupled regenerative catalytic mechanism. Figure 2.85 depicts the dependence of the azobenzene net peak current with the concentration of the chlorate ions used as an oxidant. Different curves in Fig. 2.85 correspond to different adsorption strength of the redox couple that is controlled by the content of acetonitrile in the aqueous electrolyte. In most of the cases, parabolic curves have been obtained, in agreement with the theoretically predicted effect for the surface catalytic reaction shown in Fig. 2.81. In a medium containing 50% (v/v) acetonitrile (curve 5 in Fig. 2.85) the current dramatically increases, confirming that moderate adsorption provides the best conditions for analytical application. 

The applicability of the foregoing procednre has been tested by modeling simple reaction under semi-infinite diffusion conditions (reaction 1.1) and EC mechanism coupled to adsorption of the redox couple (reaction (2.177)) [2]. The solutions derived by the original and modified step-function method have been compared in order to evaluate the error involved by the proposed modification. As expected, the precision of the modified step-function method depends solely on the value of p, i.e., the number of time subintervals. For instance, for the complex EC mechanism, the error was less than 2% for p>20. This slight modification of the mathematical procedure has opened the gate toward modeling of very complex electrode mechanisms such as those coupled to adsorption equilibria and regenerative catalytic reactions [2] and various mechanisms in thin-film voltammetry [5-7]. 

As mentioned above, it is difficult to find organic compounds which are suitable as redox catalysts for oxidations. This is the case because organic cation radicals, which are mostly the active forms in indirect electrochemical oxidations, are usually easily attacked by nucleophiles, thus eliminating them from the regenerative cycle. Therefore, the cation radicals must be stabilized towards the reaction with nucleophiles. Nelson et al. demonstrated that the cation radicals of triaryl amines and related compounds are very stable if the para positions of the aryl... 

The mechanism and kinetics of the WGS reaction over Fe-Cr catalysts have been the subject of numerous publications. Despite intense investigations, still there is no full agreement as to the reaction mechanism. The two competing approaches are a redox (regenerative) mechanism first proposed by Kulkova and Temkin as early as 1949 which presumes reduction of an oxide center (O) by a CO molecule yielding CO2 and a vacant surface center ( ), followed by reoxidation of the vacant center by water that produces hydrogen and regenerates the oxide center for the catalytic cycle. 

Figure 1.8 Cell schematics for a regenerative solar cell based on (a) an n-type photoelectrode (b) ap-type photoelectrode. The top diagrams show the cell reactions under illumination, the middle diagrams the electronic energy levels and band bending, and the bottom diagrams the cell current-voltage (I-U) characteristics with the photoelectrode and counter electrode (CE) currents shown in the same quadrant. The maximum power point is located at the point on the current-voltage curve at which the rectangle of maximum area may be inscribed in this quadrant. The photovoltage V, the electron and hole quasi-Fermi levels E and fip and the solution Fermi level f o.R, the open-circuit potential Ugc of the photoelectrode and the standard redox potential 17 ° of the 0,R redox couple are also shown.

Measurements with crystals of moderate photoelectrical quality non-specific reaction with holes specific photoreaction e.g. with C) photocurrents shift characteristically with redox potential photointercalation solar energy conversion and storage regenerative electrochemical solar cells photodecomposition of HI into jHj + photoelectroanalytical probe. 

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