Efficient one-pot transformation of furfural to pentanediol over Cu-modified cobalt-based catalysts.

Pentanediols are substances with significant market potential as the key monomers for advanced polymeric materials. In this study, we successfully achieved directly hydrogenolysis of biomass-based furfural to 1,5-pentanediol with a remarkable yield of 53.4 % using Cu-modified cobalt supported on cerium dioxide catalysts. Through comprehensive characterization techniques, including H2-TPR, NH3-TPD, XPS, EPR and Raman analysis, the study revealed that the introduction of Cu altered the dispersion of Co species, attenuated the interaction between Co species and cerium dioxide, enhanced its reduction extent, and fostered the formation of plentiful cobalt oxide species and oxygen vacancies on the catalyst's surface. The cooperative influence of Cu and Co heightened the selectivity of the hydrogenolysis reaction. This work provides a novel strategy for the development of greener and more efficient catalytic processes based on non-precious metals that for the selective conversion of biomass-derived furfural to high-value pentanediols.

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

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.