Subnanometric Cu clusters on atomically Fe-doped MoO₂ for furfural upgrading to aviation biofuels

Single cluster catalysts (SCCs) are considered as versatile boosters in heterogeneous catalysis due to their modifiable single cluster sites and supports. In this work, we report subnanometric Cu clusters dispersed on Fe-doped MoO₂ support for biomass-derived furfural upgrading. Systematical characterizations suggest uniform Cu clusters (composing four Cu atoms in average) are homogeneously immobilized on the atomically Fe-doped ultrafine MoO₂ nanocrystals (Cu₄/Fe_0.3Mo_0.7O₂@C). The atomic doping of Fe into MoO₂ leads to significantly modified electronic structure and consequently charge redistribution inside the supported Cu clusters. The as-prepared Cu₄/Fe_0.3Mo_0.7O₂@C shows superior catalytic performance in the oxidative coupling of furfural with C₃~C₁₀ primary/secondary alcohols to produce C₈~C₁₅ aldehydes/ketones (aviation biofuel intermediates), outperforming the conventionally prepared counterparts. DFT calculations and control experiments are further carried out to interpret the structural and compositional merits of Cu₄/Fe_0.3Mo_0.7O₂@C in the oxidative coupling reaction, and elucidate the reaction pathway and related intermediates.