Selective hydrogenolysis of the Csp-O bond in the furan ring using hydride-proton pairs derived from hydrogen spillover.

Selective hydrogenolysis of biomass-derived furanic compounds is a promising approach for synthesizing aliphatic polyols by opening the furan ring. However, there remains a significant need for highly efficient catalysts that selectively target the Csp-O bond in the furan ring, as well as for a deeper understanding of the fundamental atomistic mechanisms behind these reactions. In this study, we present the use of Pt-Fe bimetallic catalysts supported on layered double hydroxides [PtFe /LDH] for the hydrogenolysis of furanic compounds into aliphatic alcohols, achieving over 90% selectivity toward diols and triols. Our findings reveal that the synergy between Pt nanoparticles, atomically dispersed Pt sites and the support facilitates the formation of hydride-proton pair at the Pt ⋯O Lewis acid-base unit of PtFe /LDH through hydrogen spillover. The hydride specifically targets the Csp-O bond in the furan ring, initiating an S2 reaction and ring cleavage. Moreover, the presence of Fe improves the yield of desired alcohols by inhibiting the adsorption of vinyl groups, thereby suppressing the hydrogenation of the furan ring.