Ru-Based Water Oxidation Catalysts : Development and Mechanistic Studies

Abstract: Oxidation of water constitutes one of the most challenging processes in artificial photosynthesis, which aims at storing solar energy in the form of chemical bonds of high-energy fuels. To facilitate this process, efficient and durable water oxidation catalysts have to be developed and integrated into the complete photosynthetic cells. Importantly, the intricate complexity of such devices requires the catalyst not only to be highly efficient and robust, but also operate through a well-defined mechanism.This thesis describes the development and mechanistic studies of new water oxidation catalysts based on ruthenium. The first part of the thesis describes the synthesis of a dinuclear ruthenium-based catalyst active for both chemical and light-driven water oxidation. This catalyst displayed a pronounced influence of the acetonitrile co-solvent on the redox properties, which was studied in detail by electrochemical methods. In the second part, a new benzimidazole-based mononuclear catalyst was evaluated. The activity of the catalyst was studied for chemical and light-driven water oxidation, and insight into the operating mechanism was provided with the help of density functional theory calculations. In the third part of the thesis, a new mononuclear ruthenium-based catalyst was prepared and evaluated for electrochemically-driven water oxidation. This catalyst displayed activity similar to that of the current state-of-the-art water oxidation catalyst, while eliminating its main drawback, that is incomplete activation. The redox properties of the new catalyst were studied in detail by electrochemical and spectroscopic techniques, providing insight into the origins of its improved performance. Finally, in the fourth part of the thesis, a heterogeneous nanoparticulate catalyst immobilized on a solid support is described. The catalyst displayed high activity and stability during chemical and light-driven water oxidation, which was attributed to the small average particle size and efficient anchoring of the catalyst to the heterogeneous support via an oxidatively-stable linker.