ABSTRACT The selective hydrogenative rearrangement of biomass-derived 5-hydroxymethylfurfural (HMF) to 3-hydroxymethyl-cyclopentanone (HCPN) remains a significant challenge in biomass valorization owing to complex reaction pathways and demanding reaction conditions. Here, we report a carbon-supported bimetallic CoZn catalyst synthesized through the thermal decomposition of a CoZn–citrate complex. A high HCPN yield of 86.3% is achieved at 140 °C under 1 MPa H 2 , significantly outperforming monometallic Co@C (46.6%) and Zn@C (0%) under identical conditions. Characterization and mechanistic studies revealed that the excellent catalytic performance of CoZn@C(1:1) is a result of the synergistic effects of multiple active catalytic sites (Co 3 O 4 , ZnO, and Co 0 ). ZnO modulates the adsorption configuration of HMF by weakening furan-ring interactions with Co 0 , while balancing acidity and hydrogenation activity to suppress side reactions. This balanced catalytic environment favors the Lewis acid (Co δ+ ) mediated rearrangement pathway. Additionally, the catalyst demonstrated applicability for other biomass derived furan aldehydes, with furfural selectively converted to cyclopentanone with 91.4% yield. This work presents an effective strategy for designing non-noble bimetallic catalysts as alternatives to noble-metal catalysts for biomass valorization applications.
Ku et al. (Mon,) studied this question.