P-induced electron transfer interaction for enhanced selective hydrogenation rearrangement of furfural to cyclopentanone

Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization. Herein, we reported a P-doping bifunctional catalyst (Ni-P/mSiO2) that achieved 96.6% yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions (1 MPa H2, 150 degrees C). The turnover frequency of Ni-P/ mSiO2 was 411.9 h-1, which was 3.2-fold than that of Ni/mSiO2 (127.2 h-1). Detailed characterizations and differential charge density calculations revealed that the electron-deficient Nip+ species were generated by the electron transfer from Ni to P, which promoted the ring rearrangement reaction. Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone. This work unraveled the connection between the localized electronic structures and the catalytic properties, so as to provide a promising reference for designing advanced catalysts for biomass valorization. (c) 2024 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.