Computational Insight into Selective Hydrogenolysis over Monomeric MoO x -Modified Rh Catalysts in the Aqueous Phase

K Takei and T Ikeda and K Muraoka and Y Nakagawa and K Tomishige and A Nakayama, JOURNAL OF PHYSICAL CHEMISTRY C, 129, 5361-5368 (2025).

DOI: 10.1021/acs.jpcc.4c08142

The reaction mechanism of hydrogenolysis over monomeric MoO x -modified Rh catalysts is investigated by density functional theory-based molecular dynamics simulations. By explicitly treating the surrounding water molecules, the free energy surfaces are constructed for the aqueous-phase hydrogenolysis reaction. Ethylene glycol is employed as a model substrate, and it is shown that the attack of surface hydride-like species on the carbon atom at a position adjacent to the alkoxide ad- species via the SN2 reaction facilitates the cleavage of the C-O bond and it is more efficient than the attack on the carbon atom of alkoxide ad-species. Our study of the SN2 mechanism of the Rh-MoO x catalyst offers insight into the reaction mechanism of hydrogenolysis in the aqueous phase for metal nanoparticles modified with metal-oxide species and the design of selective catalysts for hydrogenolysis and other related reactions of biomass-derived feedstocks.

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