Overcoming Site Blocking through MoO _<i>x</i> Modification for Efficient Continuous Aqueous-Phase Hydrogenation-Rearrangement of Furfural

The catalytic hydrogenation-rearrangement of furfural (FFA) to cyclopentanone (CPO) and cyclopentanol (CPL) holds significant promise for biomass upgrading and the valorization of renewable resources. However, the complexity of the reaction network makes product selectivity highly sensitive to catalyst concentration. Under high catalyst loading, basic sites inhibit the protonation step of furfuryl alcohol (FA), which limits the feasibility of continuous production in fixed-bed reactors. In this study, we constructed a Mo/CuZnZr catalyst via a controlled MoOx modification strategy for catalyst-intensive systems, which efficiently catalyzed the hydrogenation-rearrangement of FFA to CPO and CPL in a continuous-flow reactor, achieving a total yield of 82.6% and demonstrating excellent stability over a 300-h long-term operation. Detailed experimental investigations revealed that atomically dispersed Mo species preferentially occupy basic hydroxyl sites on ZrO2, forming Zr–O–Mo bonds that reconstruct the acidity of the catalyst and enhance the protonation of FA under high catalyst loading. This study presents a feasible strategy for continuously upgrading FFA and highlights the potential of rational catalyst design in the selective transformation of biomass-derived platform molecules.