Oxophilicity-Driven Room-Temperature C─O Cleavage Over Single-Atom W-Doped MoS2.

The efficient cleavage of C─O bonds under mild conditions is essential for biomass upgrading yet remains challenging due to their kinetic inertness. Conventional MoS2 catalysts require elevated temperatures or high sulfur-vacancy densities to achieve meaningful activity. Here, we demonstrate that single-atom tungsten substitution in MoS2 (W-MoS2) 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-MoS2 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 MoS2. This work establishes oxophilicity engineering as a powerful strategy to unlock the intrinsic potential of two-dimensional sulfides for room-temperature biomass refining.