Synergy between Ni3Sn2 alloy and Lewis acidic ReOx 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, Ni 3 Sn 2 -ReO x /TiO 2 is synthesized via successive impregnation and exhibits full conversion and 92.5 % CPO selectivity under 3.0 MPa H 2 at 140 °C, which are much higher than those of Ni/TiO 2 and Ni 3 Sn 2 /TiO 2 . Characterizations show that Ni 3 Sn 2 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 Ni 3 Sn 2 and shifts its adsorption configuration, which consequently inhibits side reactions and favors the metal-acid (Ni 3 Sn 2 -ReO x ) synergy. The catalyst is stable, recyclable and also active at even 0.5 MPa H 2 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.