Oxygen Vacancies Enrichment in Citric Acid-Assisted Synthesis of Zirconia Supported Ni Catalyst for Highly Selective Hydrogenolysis of 5-Hydroxymethylfurfural.

Abstract

2, 5-Dimethylfuran (DMF), which is a promising new-generation liquid biofuel, has attracted widespread attention owing to the sustainability of biomass-derived energy sources. In this study, a highly dispersed zirconia-supported nickel catalyst (CA-Ni/ZrO2) was prepared via citric acid-assisted wetness impregnation for the selective hydrogenolysis of 5-hydroxymethylfurfural (HMF) to produce DMF. The characterization results confirmed the presence of Zr3+ species in the mesoporous CA-Ni/ZrO2 catalyst and the formation of oxygen vacancies during its preparation, which led to the formation of a large number of catalytically active sites for the adsorption and activation of the C=O/C-O groups. Under appropriate reaction parameters, an excellent DMF selectivity of 99.1 % and an HMF conversion of 98.4 % were achieved. A suitable kinetic model revealed that DMF was preferentially formed via the 2,5-dihydroxymethylfuran intermediate route, although a 5-methylfurfural route was also observed. Additionally, the interaction between Ni and ZrO2 significantly affected the stability of the catalyst. This study will provide guidelines for optimizing the catalytic conversion of furan derivatives over heterogeneous catalysts.