Phosphate-supported palladium single atom and nanoparticle boost ambient temperature tandem hydrogenolysis–hydrogenation of furan alcohols/aldehydes

Developing a one-pot method for tandem hydrogenolysis–hydrogenation of biomass-derived furan-based alcohols to methyltetrahydrofurans is challenging but crucial for synthesizing sustainable biofuels and chemicals. Herein, we report the efficient hydrogenolysis–hydrogenation of furan alcohol to 2-methyltetrahydrofuran using a phosphate-supported synergistic palladium single atom and nanoparticle at an ambient temperature. Comprehensive characterizations and theoretical calculations reveal that in situ H2 heterolysis at the palladium single atom–AlPO4 interface generates frustrated Lewis H+–H− pairs, which selectively cleaves the C–OH bond in furan alcohol to form 2-methylfuran, and H atoms on the palladium nanoparticle surface promotes the subsequent CC hydrogenation of 2-methylfuran to 2-methyltetrahydrofuran. Additionally, the catalyst shows generality for various furan and heterocyclic alcohols. Furthermore, the catalyst exhibits excellent activity in the hydrogenation–hydrogenolysis–hydrogenation of furan aldehydes to methyltetrahydrofurans. The results provide a highly efficient reaction for synthesizing methyltetrahydrofurans at ambient temperature, which has excellent potential for industrial applications.