Modeling solvent effects in catalytic reactions for energy conversion

Development of a hydrogen economy is a promising path to address increasing global energy needs. Methanol dehydrogenation and (photo)electrochemical water oxidation are important reactions in this regard. To develop and design active catalysts for these reactions, it is beneficial to have a detailed and accurate understanding of the reaction mechanism under operando conditions, which is a challenge. In this thesis, we demonstrate how our approach of using finite-temperature ab-initio molecular dynamics simulations with an explicit description of the solvent provide novel insights into the reaction mechanism for water oxidation and aqueous methanol dehydrogenation catalyzed by ruthenium (Ru) based molecular complexes and (photo)electrochemical water oxidation catalyzed by titanium dioxide (TiO₂) surfaces. The solvent molecules are shown to play an active role in these reactions by participating via hydrogen bonding, donating protons, or mediating proton-transfer processes, thereby affecting the thermodynamics, kinetics and the overall nature of the reaction mechanism. The results presented in this thesis stress on the importance of such a modeling approach for an accurate understanding of catalytic reactions in complex reaction environments.