Efficient synthesis of the liquid fuel 2,5-dimethylfuran from biomass derived 5-(chloromethyl)furfural at room temperature

The synthesis of renewable transportation fuel 2,5-dimethylfuran (DMF) from biomass is a promising solution for efficient alleviating the dependence on the petroleum-derived commodities. Here, we found that in-situ gener-ation of acidic species and Pd-Cl active sites bring high selectivity and activity towards hydrogenolysis of biomass-derived 5-(chloromethyl)furfural (CMF) to DMF. Gratifyingly, 92% DMF yield was achieved from CMF for 15 min, which indicates that space-time-yield is at least one order of magnitude higher than previous literature employed 5-hydroxymethylfurfural (HMF) as substrate. Kinetic studies showed that the in-situ formed acid has ignorable negative effect on polymerization of substrate to humins. DFT explicitly elucidate that the decorated Pd nanoparticles by Cl species provided lower adsorption energy and energy of C-O cleavage than Pd sites. Furthermore, the strategy of in-situ formation of homogeneous acid and halogen-modified metal is also efficient for catalytic conversion of other chlorinated carboxides to hydrocarbons with the ring intact.