Oxophilicity‐Driven Room‐Temperature C─O Cleavage Over Single‐Atom W‐Doped MoS 2

The efficient cleavage of C─O bonds under mild conditions is essential for biomass upgrading yet remains challenging due to their kinetic inertness. Conventional MoS 2 catalysts require elevated temperatures or high sulfur‐vacancy densities to achieve meaningful activity. Here, we demonstrate that single‐atom tungsten substitution in MoS 2 (W‐MoS 2 ) dramatically enhances the intrinsic activity of edge sulfur vacancy sites for room‐temperature hydrodeoxygenation of 5‐hydroxymethylfurfural (HMF). The oxophilic W centers elongate C─O bonds through strong oxygen coordination and lower the C─O bond cleavage barrier, leading to a three‐fold increase in turnover frequency. The optimized W‐MoS 2 catalyst delivers complete HMF conversion with 100% selectivity toward a C6 fuel blend (a mixture of 2,5‐dimethylfuran and 1,2‐bis(5‐methyl‐2‐furanyl)ethylene) under near‐ambient conditions. Notably, full HMF conversion is achieved even at room temperature, with a reaction rate constant three times that of pristine MoS 2 . This work establishes oxophilicity engineering as a powerful strategy to unlock the intrinsic potential of two‐dimensional sulfides for room‐temperature biomass refining.