Discovery of a New Solvent Co-Catalyzed Mechanism in Heterogeneous Catalysis: A First-Principles Study with Molecular Dynamics on Acetaldehyde Hydrogenation on Birnessite.

ABSTRACT: Heterogenous hydrogenation reactions are essential in a wide range of chemical industries. In this work, we find that the hydrogenation of acetaldehyde on birnessite cannot occur through the traditional mechanisms due to the strong adsorption of the aldehyde and hydrogen on the surface, using first-principles calculations. We discover that this reaction can occur feasibly via a solvent-cocatalyzed mechanism with molecular hydrogen in the liquid phase: a methanol solvent or a similar solvent is required for the reaction. Free energy calculations shows that the methanol solvent preferentially fills the oxygen vacancies of the catalyst surface and spontaneously dissociates on the surface, in which the resulting hydroxyl group then acts as the coordination site for the carbonyl bond and allows

SUBMITTER: Xie W 

PROVIDER: S-EPMC8889551 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature