Active site cooperativity in nickel hetero-valent interface on tungsten oxide for selective hydrogenative ring-rearrangement of furfural to cyclopentanone

Cyclopentanone (CPO) as a key raw material has been widely applied in spices, pharmaceuticals, and sustainable fuels. The catalytic conversion of biomass-derived furfural (FAL) to CPO meets the requirements of sustainable development goal but still be challenging because of the relatively low selectivity of CPO in the complex tandem catalytic processes. Herein, a Ni/WO 3 -H 2 catalyst presents a cooperative interface that possesses hetero-valent interface of Ni 0 (metallic) and Ni 2+ (interfacial NiWO 4 ), oxygen vacancies (O v ), and acid sites simultaneously was prepared and applied in the tandem hydrogenative ring-rearrangement of FAL to CPO. Under 160 °C and 3 MPa of initial hydrogen pressure, the catalyst achieved 90.3 % furfural conversion and 96.9 % selectivity to CPO, with a turnover rate of 4.26 mmol·g cat ⁻¹ ·h⁻¹ . Moreover, the Ni/WO 3 -H 2 catalyst demonstrated excellent stability and recyclability. Further investigation on reaction mechanism shows that the synergy of each active site, Ni 0 , Ni 2+ (NiWO 4 ), oxygen vacancies (O v ), and acid sites, promotes the conversion of FAL to CPO and effectively avoids the undesired side reaction. Accordingly, a multi-site cooperative mechanism is proposed: FAL hydrogenates to FOL on Ni 0 sites; acid sites rearrange FOL to HCP, which dehydrates at O v sites to CPE; ultimately, CPE is hydrogenated to CPO on Ni hetero-valent interface.