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 C[dbnd]C 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.