A switchable hydrogenation chemoselectivity of biomass platform compounds based on solvent regulation

Selective catalytic conversion of biomass-derived compounds to fuels and fine chemicals serves as a renewable energy pathway for the partial substitution of fossil resources, in which reaction pathway and selectivity control are key issues. Herein, we report a fully exposed Pt clusters immobilized on CoAl mixed metal oxides catalyst (denoted as Ptn/CoAl-MMOs), which exhibits prominent catalytic performance towards liquid phase hydrogenation reaction of furfural (FAL). Noteworthily, the hydrogenation chemoselectivity can be switched among four products via using four different solvents: tetrahydrofurfuryl alcohol (THFA; yield: 91.4%), furfuryl alcohol (FA; yield: 97.7%), 2-methylfuran (2-MF; yield: 92.1%) and furan (FU; yield: 90.8%) are obtained in ethanol, dioxane, isopropanol and n-hexane solvent, respectively. Experimental studies (in situ FT-IR and TPSR-Mass) combined with theoretical calculations (DFT) reveal that solvent molecules exert an essential influence on the adsorption configuration of FAL via changing the solvent-catalyst and/or substrate-catalyst interaction, which ultimately determines the hydrogenation pathway, key intermediate and final product. This work demonstrates a facile solvent-dependent product-switching strategy within one catalytic system, which opens up potential opportunities for tailoring hydrogenation selectivity in liquid-solid catalytic reactions towards biomass upgrading.