Catalytic Hydrogenation of HMF over Nitrogen-Phosphorus-Sulfur Tri-Doped Molybdenum-Based Catalysts

Abstract

This work presents a novel "one-pot" method for synthesizing tri-doped catalysts, successfully constructing a nitrogen, phosphorus, and sulfur tri-doped molybdenum-based catalyst (NPS-Mo). The synergistic effects between Mo and multiple heteroatoms on the hydrogenation of 5-hydroxymethylfurfural (HMF) were systematically investigated, thereby achieving a high 5-methylfurfural (5-MF) selectivity of 97.6% and a high space-time yield (STY) of 974.7 mg•g⁻¹cat•h⁻¹ under atmosphericpressure fixed-bed conditions. Dynamic characterization and analysis revealed that the co-coordination of N, P, and S constitutes the origin of the high catalytic activity, with the high-entropy effect induced by the multi-element system further contributing to enhanced catalytic performance. DFT calculations further demonstrate that the co-coordination by N, P, and S optimizes the adsorption energies of H₂ and HMF on the active sites.