Processes Caused by Photoexcitation of Reactants in the Solution

If a solution, being in contact with an electrode, contains photosensitive atoms or molecules, irradiation of such a system may lead to photoelectro-chemical reactions or, to be more exact, electrochemical reactions with excited particles involved. In such reactions the electrons pass either from an excited particle to the electrode (the anodic process) or from the electrode to an excited particle (the cathodic process). In this case, an elementary act of charge transfer has much in common with ordinary (dark) electrochemical redox reactions, which opens a possibility of interpreting certain aspects of photochemical processes under consideration with the use of concepts developed for general quantum mechanical description of electrode processes. 

In the case of a semiconductor electrode, the existence of the energy gap makes a qualitatively different location of energy levels quite probable (Figs. 23b, 23c). One of them, either the ground or excited, is just in front of the energy gap, so that the direct electron transition with this level involved appears to be impossible. This gives rise to an irreversible photoelectro-chemical reaction and, as a consequence, to photocurrent iph. The photoexcited particle injects an electron into the semiconductor conduction band 

Finally, in an insulator (a very wide-gap semiconductor to be exact) there is a large probability of an inverse, with respect to metal, limiting case (Fig. 23d). Here the energy gap is so wide that it exceeds considerably the energy of 

Regeneration of consumed (i.e., given off an electron to the electrode or, on the contrary, acquired an electron) photoactive substance (sensitizer) in the solution is a very important matter from the practical point of view. As soon as all the near-the-electrode (adsorbed) layer of this substance is oxidized (or reduced) the photoprocess ceases. To obtain a continuous photocurrent, the amount of the initial reactant, sensitizer, near the electrode surface should be renewed. 

Photosensitive substances adsorbed on the semiconductor surface are especially efficient in sensitization reactions. Thus, sensitizing effect can be enhanced if a sensitizer is attached to the semiconductor surface by a chemical bond. For this purpose one has to create either the ether bond -O-between the semiconductor and reactant, using natural OH groups, which exist on the surface of, for example, oxide semiconductors (Ti02, ZnO) or oxidized materials (Ge, GaAs, etc.) in aqueous solutions, or the amide bond -NH- in the latter case a monolayer of silane compounds with amido-groups is preliminarily deposited on the semiconductor surface (see, for instance, Osa and Fujihira, 1976). With such chemically modified electrodes the photocurrent is much higher than with ordinary (naked) semiconductor electrodes. 

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