Edge Sulfur Vacancies on MoS₂ Enable Room-Temperature Hydrodeoxygenation of 5-Hydroxymethylfurfural

Selective hydrodeoxygenation (HDO) of biomass-derived platform molecule 5-hydroxymethylfurfural (HMF) to synthetic chemicals and liquid biofuels with high activity and selectivity is attractive yet challenging, especially at low temperature. Herein, we report a highly active and selective MoS₂ catalyst (denoted as MoS₂-T) enriched with edge sulfur vacancies by using a modified hard template method, which displays a high yield of 97.2% toward C6 fuel blend (mixture of 2,5-dimethylfuran (DMF) and 1,2-bis(5-methyl-2-furanyl)ethylene (BMFE)) in the HDO of HMF at 70°C. In particular, the activity of HMF conversion could be reached up to 100% with prolonged reaction time even at room temperature. A combination of H-D exchange, KIE experiments, and density function theory studies indicates that the abundant edge sulfur vacancies on MoS₂-T facilitate the activation and dissociation of H₂ as well as the cleavage of C─O bonds, thus accounting for the high activity of HMF conversion at near-ambient-temperature. The vacancy engineering strategy developed in this work offers a new approach for designing efficient, low-cost non-noble metal catalysts for producing furan-based fuels from biomass.