Edge Sulfur Vacancies on MoS ₂ Enable Room‐Temperature Hydrodeoxygenation of 5‐Hydroxymethylfurfural

ABSTRACT 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 MoS 2 catalyst (denoted as MoS 2 ‐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 MoS 2 ‐T facilitate the activation and dissociation of H 2 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.