Synergy between Ni₃Sn₂ alloy and Lewis acidic ReO_x enables selectivity control of furfural hydrogenation to cyclopentanone

Selectivity controlling is a crucial and challenging issue for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). Herein, Ni₃Sn₂-ReO_x/TiO₂ is synthesized via successive impregnation and exhibits full conversion and 92.5 % CPO selectivity under 3.0 MPa H₂ at 140 °C, which are much higher than those of Ni/TiO₂ and Ni₃Sn₂/TiO₂. Characterizations show that Ni₃Sn₂ is the main active phase that remarkably restrains the over-hydrogenation of the furan ring, while ReO_x plays an electrophile or Lewis acid site to activate C-OH of furfuryl alcohol and induces its rearrangement. DFT calculations verify that Sn doping weakens the furan ring adsorption on Ni₃Sn₂ and shifts its adsorption configuration, which consequently inhibits side reactions and favors the metal-acid (Ni₃Sn₂-ReO_x) synergy. The catalyst is stable, recyclable and also active at even 0.5 MPa H₂ and 80 °C. This study provides an advanced strategy for the rational design of superior catalysts for tuning product selectivity, with practical potential for upgrading biomass-derived platform molecules. © 2023 Elsevier B.V.