Enhanced Cyclopentanone Yield from Furfural Hydrogenation: Promotional Effect of Surface Silanols on Ni-Cu/m-Silica Catalyst

Abstract

A direct alkaline hydrothermal method was used to synthesize mono- and bimetallic Ni and Cu on mesoporous silica (m-SiO2) as catalysts for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). The catalysts were characterized by XRD, FTIR, H2-TPR, SEM, TEM, HR-TEM, XPS, ICP, BET, and CHN analysis. The results demonstrate that the addition of Cu metal improved the reducibility of Ni catalysts and revealed Ni-Cu alloy formation over m-SiO2. Furthermore, XPS and FTIR results reveal that the silanol groups on the catalyst surface play an important role in the ring rearrangement of furfuryl alcohol. Hence, the effect of silanol groups in the FOL rearrangement was studied in detail. Among the catalysts at fixed metal loading of 20 wt.%, Ni5Cu15/m-SiO2 catalyzed the formation of CPO as the main product due to the synergy of Ni-Cu alloy and surface silanol groups. Ni5Cu15 supported on a commercial mesoporous silica (Ni5Cu15/C-SiO2) showed inferior performance compared with the Ni5Cu15/m-SiO2 catalyst for the FAL hydrogenation. Reaction temperature and time were also optimized for the enhanced CPO yield over Ni5Cu15/m-SiO2. The Ni5Cu15/m-SiO2 catalyst is durable, as demonstrated by stability tests over multiple reuses. This effective and flexible NixCuy on m-SiO2 catalyst provides an effective candidate for efficient upgrading of furanics in selective hydrogenation reactions.