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℃). The turnover frequency of Ni-P/mSiO2was 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 Niδ+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.