Photoanode anodic decomposition

One additional problem at semiconductor/liquid electrolyte interfaces is the redox decomposition of the semiconductor itself.(24) Upon Illumination to create e- - h+ pairs, for example, all n-type semiconductor photoanodes are thermodynamically unstable with respect to anodic decomposition when immersed in the liquid electrolyte. This means that the oxidizing power of the photogenerated oxidizing equivalents (h+,s) is sufficiently great that the semiconductor can be destroyed. This thermodynamic instability 1s obviously a practical concern for photoanodes, since the kinetics for the anodic decomposition are often quite good. Indeed, no non-oxide n-type semiconductor has been demonstrated to be capable of evolving O2 from H2O (without surface modification), the anodic decomposition always dominates as in equations (6) and (7) for... 

Fig. 7.7 Percentage of photogenerated holes that contribute to anodic decomposition versus O2 evolution from naked (no catalyst), Pt-coated, and polymer-Pt coated n-CdS photoanode in 0.5 M Na2S04 solution (pH = 8.6) [14].

N-type semiconductors can be used as photoanodes in electrochemical cells Q., 2, 3), but photoanodic decomposition of the photoelectrode often competes with the desired anodic process (1 4 5). When photoanodic decomposition of the electrode does compete, the utility of the photoelectrochemical device is limited by the photoelectrode decomposition. In a number of instances redox additives, A, have proven to be photooxidized at n-type semiconductors with essentially 100% current efficiency (1, 2, 3, 6>, ], 8, 9). Research in this laboratory has shown that immobilization of A onto the photoanode surface may be an approach to stabilization of the photoanode when the desired chemistry is photooxidation of a solution species B, where oxidation of B is not able to directly compete with the anodic decomposition of the "naked" (non-derivatized) photoanode (10, 11, 12). Photoanodes derivatized with a redox reagent A can effect oxidation of solution species B according to the sequence represented by equations (1) - (3) (10-15). 

The kinetic law (eqn, (5)), which was found to describe the competition between the photoanodic oxidation of TMPD and that of GaAs in water + methanol mixtures with 48 and 80 mol % CH30H and in water + acetonitrile mixture with 13 mol % CH3CN, can be interpreted on the basis of a reaction mechanism in which the subsequent electrochemical steps in the anodic decomposition of the semiconductor occur by the capture of a free hole at each step (instead of by reaction with mobile intermediates X] as was the case with the mechanisms discussed before). The oxidation of the dissol ved reducing agent occurs through reaction with X] orX OH. 

Photocorrosion can be prevented by adding a redox couple to the electrolyte whose potential is more favourable than the decomposition potential such that the redox reaction occurs preferentially. When n-CdS is used as photoanode in aqueous electrolytes, the electrode is photocorroded since the reaction, CdS -1- 2h - S -1- Cd, occurs readily. By adding NaOH and sodium polysuphide to the electrolyte (Ellis et al, 1976), photocorrosion is prevented. The /S redox couple preferentially scavenges the photoholes. At the anode, sulphide is oxidized to polysulphide (free sulphur) and free sulphur is reduced back at the dark cathode. Similarly n-Si anodes have been stabilized by using a nonaqueous electrolyte containing a ferricinium/ferrocene redox couple (Legg et al, 1977 Chao et al, 1983). Unfortunately, a similar stabilization technique cannot be applied to photoelectrolysis cells. Some examples of electrode... 

A few other applications of dithiolenes make use of their redox properties. Kumar et a/.219 proposed the use of dithiolenes as photosensitizers. Umezawa et al.22<> coated a Pt cathode with (Et4N)Ni(mnt)2 and saw a modest degree (1.4 x 10 4 %) of light conversion upon irradiation. On the opposite side, Bradley et al.721 used dithiolenes to stabilize n-type Si anodes against photoanodic decomposition. 

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