Synergistic tri-site NiZnAl catalyst for aqueous-phase hydrogenation and cascade rearrangement of furfural to cyclopentanone.

The tandem catalytic conversion of furfural to cyclopentanone represents a crucial transformation in biomass valorization, yet faces persistent challenges due to competing hydrogenation and ring-opening pathways. Herein, we report the rational design of a three-dimensional flower-like hierarchical nanostructure catalyst derived from NiZnAl-layered double oxide precursors, which features well-dispersed NiZn alloy active sites. Comprehensive characterization studies reveal that Zn incorporation plays a dual role in modulating surface acidity and promoting oxygen vacancies formation through structural reconstruction. Mechanistic investigations via density functional theory calculations demonstrate that the NiZn phase optimizes the adsorption geometry of furfural molecules, while the engineered oxygen vacancies synergistically enhance H dissociation and polarize the CO group through electron transfer effects. This unique configuration effectively suppresses undesirable furan ring over‑hydrogenation. The optimized NiZnAl catalyst demonstrates exceptional performance with quantitative conversion of furfural (100 %) and remarkable cyclopentanone selectivity (97.3 %) under industrially viable conditions (160 °C, 0.5 MPa H), outperforming most reported non-noble metal catalysts. This work provides a material design strategy through multi-site synergistic engineering of metal alloys, acid-base properties, and defect structures, contributing to sustainable biomass valorization for fine chemical production.