Rational design for the fabrication of bulk Ni(3)Sn(2) alloy catalysts for the synthesis of 1,4-pentanediol from biomass-derived furfural without acidic co-catalysts

This study describes the rational design for the fabrication of bulk Ni(3)Sn(2) alloy catalysts for the de/hydration–hydrogenation of biomass-derived furfural (FFald) to 1,4-pentanediol (1,4-PeD) without the acidic co-catalyst. The presence of both hydration active sites (Brønsted acid sites (Ni–SnO(x))) and hydrogenation active sites (Ni(0) or Ni–Sn alloy) in Ni(3)Sn(2) alloy could be controlled by changing the pH of Ni–Sn solution during the preparation. Both active sites acted synergistically to catalyse the de/hydration–hydrogenation reactions of FFald to produce a high yield of 1,4-PeD in a batch reaction system at 433 K, 3.0 MPa H(2) after 12 h. Bulk Ni(3)Sn(2) obtained at pH of Ni–Sn solution of 8–10, hydrothermal temperature of 423 K for 24 h, and reduction with H(2) at 673 K for 1.5 h demonstrated a high yield of 1,4-PeD (81–87%), which is comparable with that from previous work. A 76% yield of 1,4-PeD was also obtained when the reaction was carried out in a fixed-bed reaction system at 433 K, flow rate 0.065 mL min(−1), H(2) flow rate 70 mL min(−1), and 3.29 wt% FFald in H(2)O/ethanol solution for 12 h. The activity of bulk Ni(3)Sn(2) was maintained with 66% yield of 1,4-PeD even after 52 h reaction on stream. The fabricated bulk Ni(3)Sn(2) alloy catalysts could be the promising heterogeneous Ni–Sn alloy-based catalysts for the catalytic conversion of biomass-derived-furanic compounds (e.g., FFald, furfuryl alcohol (FFalc), and 2-methylfuran (2-MeF)).