The selective hydrogenation of 5-Hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan by interfacial engineering and oxygen vacancies on CuNi/CeO2 catalyst

MOF-templated strategy fabricates highly dispersed Cu x Ni 2-x /CeO 2 catalysts. • Cu 1.2 Ni 0.8 /CeO 2 achieves 100% BHMF yield under mild reaction conditions. • Cu-O V interfacial sites induce vertical adsorption for C=O selective activation. • Ni-promoted H spillover boosts hydrogenation efficiency. Efficient utilization of biomass is a cornerstone of green chemistry and sustainable development. 5-Hydroxymethylfurfural (5-HMF) constitutes a pivotal biomass-derived platform molecule which selective hydrogenation into 2,5-bis(hydroxymethyl)furan (BHMF) plays a crucial role in the development of bio-based materials and fine chemicals. Conventional monometallic catalysts, however, are often constrained by an intrinsic trade-off between activity and selectivity and tendencies toward particle sintering and deactivation. To address these challenges, a metal–organic-framework (MOF) precursor was employed in a self-sacrificial templating route to fabricate highly dispersed, oxygen vacancies-tunable, bimetallic Cu x Ni 2–x /CeO 2 catalysts. By integrating comprehensive physicochemical characterization with in-situ spectroscopies, a systematic investigation was conducted to examine the effects of the Cu/Ni ratio and oxygen vacancy (O V ) concentration on 5-HMF hydrogenation were systematically investigated to elucidate structure–activity relationships. The results demonstrate that the Cu 1.2 Ni 0.8 /CeO 2 catalyst achieves an optimal balance between O V and metal site distribution, enabling nearly complete 5-HMF conversion and exclusive selectivity toward BHMF. Interfacial synergy facilitates Ni-mediated H 2 dissociation and hydrogen spillover to Cu sites, while the O V selectively adsorbs and activates the carbonyl of HMF, suppressing furan-ring hydrogenation and other side reactions. Compared with prior reports, this work highlights the decisive roles of O V and bimetallic interfaces in promoting substrate-selective adsorption, active-hydrogen supply, and side-reaction suppression. This strategy advances the high-value conversion of biomass platform molecules and provides a conceptual foundation for the rational design of green catalysts. Download: Download high-res image (116KB) Download: Download full-size image