Mechanistic insights into the catalytic hydrogenation of furfural derivatives over Pd and Pt catalysts - Raw Data

Furfural and its derivatives exhibit high potential as platform chemicals in the developing circular economy. To help deepen our understanding of their utility as bio-based feedstocks with high molecularity, we present an experimentally verified density functional theory (DFT) landscape of the catalytic hydrogenation of furfural-derived ketones over model Pd and Pt catalysts. Reaction mechanisms were identified for the hydrogenation of both chain C=C bonds and furan rings. Our model successfully predicts that chain double bonds are readily hydrogenated over both metals, whereas the hydrogenation of furan ring systems is strongly sensitive to catalyst choice. A low activation energy barrier of +69.1 kJ mol^-1 was observed for ring hydrogenation over Pd(111). Computational analysis revealed that the accumulation of positive charge on the furan carbons impeded ring hydrogenation over Pt(111), leading to poor activity and selectivity