Highly efficient, amorphous bimetal Ni-Fe borides-catalyzed hydrogenolysis of 5-hydroxymethylfurfural into 2,5-dimethylfuran

Abstract

Designing highly efficient non-noble metal catalyst for the selective hydrogenolysis of biomass derivatives to fuels and fine chemicals is a key pursuit for sustainable chemical industry but substantially challenging. In this contribution, we report, for the first time, the construction of amorphous bimetal Ni–Fe borides for efficient catalytic hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dimethylfuran (DMF) as a promising biofuel candidate. The as-prepared Ni1.52Fe0.36BOx catalyst afforded a near-quantitative DMF yield using ethanol as a green solvent under relatively mild operating conditions (1 MPa H2, 160 °C and 1 h), leading to an excellent DMF formation rate of 16.5 mmolDMF·gcat−1·h−1, which is 1.7–16.5 folds higher than the state-of-art nickel-based catalysts. Mechanistic investigations demonstrated that the Fe intervention is conductive to the generation of electron-enriched metal sites and powerful acidic sites in Ni1.52Fe0.36BOx catalyst, which favored the activation of hydrogen and the cleavage of C–O bond to accelerate the hydrogenolysis process. Moreover, Ni1.52Fe0.36BOx catalyst exhibited good recyclability as well as universality in the hydrogenolysis of various biomass-derived unsaturated aldehydes. This finding opens a new avenue for highly selective hydrodeoxygenation of renewable biomass feedstock to value-added chemicals with non-noble bimetal hybrids in a green and straightforward manner.