Particle size and surface chemistry in photoelectrochemical reactions at semiconductor particles

In the present paper reactions at small and large ZnS particles have been investigated. It has been shown that ethanol is selectively oxidized at large (micrometer) particles to acetaldehyde without side products by a ''two hole'' process. In the case of nanometer particles the primarily formed alpha-hydroxyethyl radicals in a ''one hole'' process undergo a secondary reaction, i.e., the dimerization and disproportionation of the free radicals. It has been shown that a two hole process on nanometer particles becomes impossible because the time interval between two successive photon absorption incidents which lead to a successful hole transfer process in a 1-nm particle is much longer than the maximum lifetime of the alpha-hydroxyethyl radicals formed in the first step. The different mechanisms of ethanol oxidation and the influence of surface chemistry are discussed in detail.