Kinetics and mechanisms of catalytic water oxidation.

Abstract

The kinetics and mechanisms of thermal and photochemical oxidation of water with homogeneous and heterogeneous catalysts, including conversion from homogeneous to heterogeneous catalysts in the course of water oxidation, are discussed in this review article. Molecular and homogeneous catalysts have the advantage to clarify the catalytic mechanisms by detecting active intermediates in catalytic water oxidation. On the other hand, heterogeneous nanoparticle catalysts have advantages for practical applications due to high catalytic activity, robustness and easier separation of catalysts by filtration as compared with molecular homogeneous precursors. Ligand oxidation of homogeneous catalysts sometimes results in the dissociation of ligands to form nanoparticles, which act as much more efficient catalysts for water oxidation. Since it is quite difficult to identify active intermediates on the heterogeneous catalyst surface, the mechanism of water oxidation has hardly been clarified under heterogeneous catalytic conditions. This review focuses on the kinetics and mechanisms of catalytic water oxidation with homogeneous catalysts, which may be converted to heterogeneous nanoparticle catalysts depending on various reaction conditions.