Semiconductor photoelectrodes

Derivatized semiconductor photoelectrodes offer a way to design photosensitive interfaces for effecting virtually any redox process. Manipulation of interfacial charge transfer processes has been demonstrated using hydrolytically unstable redox... 

In any case, no electrode material or approach fulfills the requirements for a successful photoelectrochemical process in all respects, i.e., for routine practical use hence novel materials and approaches are constantly pursued. Note that beside the robust performance needed, the most important figure of merit for a semiconductor photoelectrode used for water splitting is the photoconversion efficiency, which is... 

The photopontential also approaches to zero when the semiconductor photoelectrode is short-circuited to a metal counterelectrode at which a fast reaction (injection of the majority carriers into the electrolyte) takes place. The corresponding photocurrent density is defined as a difference between the current densities under illumination, /light and in the dark, jDARK ... 

The theoretical solar conversion efficiency of a regenerative photovoltaic cell with a semiconductor photoelectrode therefore depends on the model used to describe the thermodynamic and kinetic energy losses. The CE values, which consider all the mentioned losses can generally only be estimated the full line in Fig. 5.65 represents such an approximation. Unfortunately, the materials possessing nearly the optimum absorption properties (Si, InP, and GaAs) are handicapped by their photocorrosion sensitivity and high price. 

The conclusions from these considerations are that semiconductor photoelectrodes can be used to effect either reductions (p-type semiconductors) or oxidations (n-type semiconductors) in an uphill fashion. The extent to which reaction can be driven uphill, Ey, is no greater than Eg, but may be lower than Eg owing to surface states between Eqb and Eye or to an Inappropriate value of Ere(jox. Both Eg and Epg are properties that depend on the semiconductor bulk and surface properties. Interestingly, Ey can be independent of Ere(jox meaning that the choice of Ere(jox and the associated redox reagents can be made on the basis of factors other than theoretical efficiency, for a given semiconductor. Thus, the important reduction processes represented by the half-reactions (3)-(5) could, in principle, be effected with the same efficiency at a Fermi level pinned (or... 

N.S. Lewis, Chemical control of charge transfer and recombination at semiconductor photoelectrode surfaces,... 

Photoelectrochemical cells based on semiconductor photoelectrodes are potential candidates for low cost, large area, conversion devices. The basic starting materials are inexpensive and photoelectrodes of large area can be produced by electrodeposition. 

These properties of the semiconductor photoelectrode render photo-electrochemical cells useful as solar energy converters. 

ZnS-CdS (bandgap = 2.3-2.4 eV) composite semiconductor photoelectrodes show a broad spectral response and n-type behavior, with saturation of the anodic photocurrent upon increasing anodic potential making the system suitable for use as a photoelectrochemical cell photoanode [72], Nanostructured ZnS-CdS thin film electrodes show that anodic photocurrent saturation can be attained with the application of a small, 0.1 V, bias [73], while hydrogen evolution is observed at the Pt cathode. The performance of the ZnS-CdS photoanodes appear strongly dependent upon the method of film preparation [72,73], with Zn rich films demonstrating superior photocurrent generation, and stability, in comparison to Cd rich films. 

Torimoto T, Naohiro T, Nakamura H, Kuwabata S, Sakata T, Mori H, Yoneyama H (2000) Photoelectrochemical properties of size-quantized semiconductor photoelectrodes prepared by two-dimensional cross-linking of monodisperse CdS nanoparticles Electrochim Acta 45 3269-3276... 

On the other hand, oxide semiconductor materials such as ZnO and 2 have good stabilities under irradiation in solution. However, such stable oxide semiconductors cannot absorb visible light because of their wide band-gap character. Sensitization of wide-band-gap oxide semiconductor materials by photosensitizers, such as organic dyes which can absorb visible light, has been extensively studied in relation to the development of photography technology since the middle of the nineteenth century. In the sensitization process, dyes adsorbed onto the semiconductor surface absorb visible light and excited electrons of dyes are injected into the conduction band of the semiconductor. Dye-sensitized oxide semiconductor photoelectrodes have been used for PECs. 

Table 3 Photovoltaic Performance of DSSC Using Different Oxide Semiconductor Photoelectrode...

---