Strong Metal Support Interaction in Ru/V 2 O 3 Mitigates Reactant Induced Poisoning in Succinic Acid Hydrogenation

Abstract Hydrogenation of carboxylic acids to lactones is an important reaction. However, strong adsorption of carboxylic acid on the catalyst causes poisoning of the active site and demands harsher reaction conditions and organic solvents. In this study, we demonstrate that strong metal support interaction (SMSI) and hydrogen spillover on Ru/V 2 O 3 can counter such a poisoning effect. The catalyst with SMSI was able to hydrogenate succinic acid to γ‐butyrolactone (GBL) in 77% yield in the presence of water at mild conditions of 150 °C. The H 2 ‐D 2 exchange experiment showed that for Ru/V 2 O 3 catalysts reduced at higher temperatures, SMSI created a barrier between the substrate and the hydrogen dissociation sites. Moreover, the spillover of dissociated H 2 onto the V 2 O 3 surface was found to enhance catalytic activity. Thermodynamic calculations using density functional theory showed that the transfer of a hydride from Ru and a proton from V 2 O 3 to the substrate has a lower reaction‐free energy compared to the transfer of two hydrogen atoms from the ruthenium surface. Additionally, the easier desorption of product from the Ru/V 2 O 3 surface increased catalytic activity. We show that SMSI can be used as an effective strategy to mitigate the poisoning of metal sites during catalytic hydrogenation of carboxylic acids.