Synergistic Effect of Oxygen Vacancies and Ni⁰ Species on the Full Hydrogenation of 5-Hydroxymethylfurfural to Non-Furanic Cyclic Diol

2,5-Bis(hydroxymethyl)tetrahydrofuran (BHMTHF), a fully hydrogenated derivative of 5-hydroxymethylfurfural (HMF), is a key monomer for constructing degradable polyester materials and offers great potential for the valorization of biobased raw materials. Herein, Ni/CeO2 catalyst was synthesized by a facile coprecipitation method, and the selective hydrogenation of HMF was excellent at mild conditions (120 °C, 1.5 MPa H2), the yield of BHMTHF was up to 90.7%. Comprehensive characterization using X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction, and Raman spectroscopy unveiled that the introduction of Ni promotes the reduction of Ce4+ to Ce3+ on the CeO2 surface and enhances the formation of oxygen vacancies. Using density functional theory calculations, the indispensable role of the synergistic interaction between Ni0 sites and oxygen vacancies in promoting the efficient transformation of HMF to BHMTHF was confirmed. This study paves the way for the design of non-noble metal catalysts, facilitating the targeted hydrogenation of biomass-derived platform compounds and the efficient production of high-value-added chemicals.