Water-enhanced bifunctional metal-acid catalyst for C=C bond hydrogenation

Abstract

Water-assisted proton shuttling can promote hydrogenation of polar functional groups, and it is generally believed that such an effect can be hardly applied to hydrogenation of C=C bonds due to the latter’s weak interaction with water. Here, we report density functional theory calculations and metadynamics simulations, through which we show a dynamic bifunctional metal-acid site that can be transformed, when interacting with water, into an active configuration for an unexpected water-enhanced proton shuttling to C=C bonds. Specially, we investigated the B(OH)3 anchored to a Ni catalyst for hydrogenation of cyclohexene in an organic solvent, which showed in experiments an increased rate by 100 times when adding a small amount of water. Metadynamics simulations suggest that a B(OH)3-H2O cluster can form on Ni(111), which promotes the proton transfer in the first hydrogenation step, while the second hydrogenation is still driven by metal-mediated direct H-transfer. The recovery process of B(OH)3-H2O also involves a proton shuttling step. We find that the boric species on the surface serve as an electron reservoir and carries the negative charge to balance the positive charge in the proton transfer steps. This work thus provides fundamental insights of this dynamic transformation process of the metal-acid interface, which can in principle be applied to many other bifunctional systems for hydrogenating non-polar unsaturated groups by engineering the interfacial charge separation.