Solvation Effects on Methanol Decomposition on Pd(111), Pt(111) and Ru(0001)

Solvation is crucial in many chemical and electrochemical processes related to alcohol conversion on metal surfaces. Particularly, understanding the dehydrogenation mechanism of methanol on solvated Pd, Pt and Ru surfaces could allow the design of efficient methanol fuel cells. The large computational cost related to adopting an explicit solvation approach into density functional theory can be reduced drastically by using implicit solvation methods. In this study, we use our recently developed continuum solvation model (MGCM) to elucidate the minimum number of explicit water molecules to add to the solvated methanol/metal surface systems to reproduce experimental data with an optimized balance between time and reliability. Our results stress the importance of adding two explicit water molecules, especially for the case of Ru surfaces. For this later system, we provide a first insight into the decomposition mechanism of methanol using first-principles calculations. Our predictions can be then a useful reference for future studies that aim at designing more efficient heterogeneous catalysis with solvents.