Theoretical design of diatomic catalysts for selective hydrodeoxygenation of furfural to 2-methylfuran

Abstract

Selective hydrodeoxygenation (HDO) of furfural to 2-methylfuran is highly promising for renewable energy and fuel upgrading. However, the coexistence of the furan ring and formyl group leads to competitive reactions, often yielding the byproduct, tetrahydrofurfuryl alcohol (THFA). Furthermore, residual oxygen species from deoxygenation tend to accumulate on the catalyst surface, inhibiting high selectivity. This study proposes a “bifunctional site” strategy by coupling oxyphilic Mo/W with hydrogenation active Group VIII transition metals to construct diatomic catalysts. This design regulates the selective adsorption and hydrogenation of CO groups while accelerating oxygen species removal. Systematic investigation of 18 TM–Mo/W combinations identified Os–Mo, Co–Mo, and Fe–Mo as the most effective catalysts. These candidates exhibit high activity for both selective CO hydrogenation and O*/OH* removal, with rate-determining step (RDS) barriers of 0.94, 0.92, and 0.85 eV, respectively. Electronic structure analysis reveals that the oxyphilic Mo/W atoms balance CO activation with surface oxygen clearance, offering a novel cooperative catalytic mechanism for multi-step HDO reactions.