Sn-promoted Ni/montmorillonite bimetallic catalyst for efficient and selective hydrogenation rearrangement of furfural to Cyclopentanone

Cyclopentanone (CPO) is a valuable cyclic ketone widely used in pharmaceuticals, fragrances, and high‑energy‑density fuels. The transformation of biomass‑derived furfural into CPO represents a sustainable alternative, yet it remains challenging due to competing reactions such as over‑hydrogenation, furan ring hydrogenation, and undesirable condensations. In this work, a bimetallic Ni 3 Sn alloy supported on organo‑modified montmorillonite (Ni 3 Sn/MK10) was designed to precisely regulate hydrogenation activity and surface acidity. Characterization results (XRD, TEM, XPS, NH 3 ‑TPD, H 2 ‑TPR) confirmed the formation of a Ni 3 Sn alloy, which modulated the electronic structure of Ni, enhanced hydrogen dissociation, and adjusted the acid site distribution. Under optimized conditions (190 °C, 3 MPa H 2 , 5 h), the Ni 3 Sn/MK10 catalyst achieved complete furfural conversion with 77.8% cyclopentanone yield and 19% cyclopentanol yield, while effectively suppressing furan ring hydrogenation and minimizing condensation side‑reactions. Control experiments and interval-time FT‑IR analysis revealed that the reversible aldol condensation between furfural and the intermediate furfuryl alcohol plays a key role in improving cyclopentanone selectivity. The catalyst maintained stable activity over four cycles, albeit with a gradual decline in yield due to carbon deposition. This work demonstrates that tailoring the hydrogenation/acidity properties through bimetallic alloy formation on a tunable clay support is an effective strategy for the selective conversion of furfural to cyclopentanone.