Efficient Transfer Hydrogenolysis of 5-Hydromethylfurfural to 2,5-Dimethylfuran over CoFe Bimetallic Catalysts Using Formic Acid as a Sustainable Hydrogen Donor

Abstract

Currently, developing high-performance non-noble metal catalysts for the conversion of biomass-derived compounds to valuable chemicals or biofuels remains a great challenge. Herein, surface CoFeOₓ-decorated bimetallic CoFe catalysts were developed via a Co–Mg–Fe layered double hydroxide precursor strategy and utilized for the transfer hydrogenolysis of 5-hydromethylfurfural (HMF) into 2,5-dimethylfuran (DMF) with the help of formic acid as the sustainable hydrogen donor. The as-fabricated CoFe bimetallic catalyst exhibited excellent catalytic performance with a high yield of DMF (>92%). Contrarily, monometallic Co-based catalyst delivered a much lower DMF yield. The structural characterizations and catalytic experiments demonstrated that the catalytic behavior of bimetallic CoFe catalysts was correlated with the appropriate combination of highly dispersed bimetallic metallic nanoparticles and abundant oxygen vacancies originating from surface CoFeOₓ species, as well as favorable surface basic sites, thereby facilitating the dehydrogenation of formic acid and improving the affinity for carbonyl reduction, which promoted the selective hydrogenation/hydrogenolysis of carbonyl or hydroxymethyl group in HMF and reaction intermediates. Furthermore, excellent structural advantages of as-fabricated CoFe catalyst, such as high alloying degree of CoFe and strong metal–support interactions, endowed it with good stability and regeneration performance. The present bimetal-defect interfacial engineering strategy may provide a potential guide for the rational design of high-performance non-noble-metal catalysts for a variety of heterogeneous catalysis processes in terms of the conversion of biomass source.