Ru‐Catalyzed Hydrogenolysis of Methanol: A Computational and Kinetics Study

Abstract

AbstractIn spite of numerous kinetic studies, the mechanism of the polyol hydrogenolysis on a Ru catalyst surface is still not fully understood. Here, the decomposition of the C1 alcohol methanol can serve as an entry to the clarification of the mechanism. Therefore, kinetic experiments using a Ru/C catalyst and periodic DFT calculations on a Ru(0001) model surface were performed. A modeling of the Ru surface revealed that the surface is most likely covered with hydrogen adsorbates under experimental conditions. On a clean Ru model surface, the overall activation barrier is lower if less dehydrogenation steps occur on the substrate methanol before the C−O bond cleavage. Transferring the results from the clean to the hydrogen‐saturated Ru surface, the pathway via CH2O O−H formation and subsequent C−O cleavage is found to be the most favorable. This study shows that the surface coverage has a significant influence on the activation barrier.