Selective C[sbnd]O bond activation of biomass-derived γ-valerolactone to biofuels over MFI-mediated Co-based synergetic catalysts.

Achieving precise selectivity control towards the sustainable production of biofuels and chemicals in biomass resources valorization via selective C-O bond activation is an important but challenging target. Herein, a selective conversion strategy of lignocellulosic-derived γ-valerolactone (GVL) using MFI-type HZSM-5 zeolite-mediated Co-based synergetic catalysts is reported. The as-synthesized Co@HZSM-5 catalyst with highly dispersed and stable Co nanoparticles inside microcrystal enables exceedingly high selectivity for the valeric biofuel production from GVL, whereas the zeolite-supported Co/HZSM-5 catalyst exhibits a selectivity switching towards pentane biofuel under otherwise identical conditions. This selectivity difference stems from the diverse synergetic catalysis between metallic Co and acidic HZSM-5 support of Co@HZSM-5 versus Co/HZSM-5 in GVL upgrading. Theoretical calculations further demonstrate the distinct ring C-O bond strength of GVL under these two Co chemical microenvironments, which is crucial to tune the C-O bond activation modes in GVL ring-opening, affording a flexible selectivity switching toward valeric- or pentane-oriented reaction channels. [Display omitted] • Highly dispersed and stable Co nanoparticles was finely encapsulated in HZSM-5. • Selectivity switching of valeric/pentane biofuels from GVL upgrading was achieved. • Diverse Co-acid synergetic effects under two Co chemical environments were found. • Well-controlled ring C-O bond activation mode in GVL ring-opening was achieved. [ABSTRACT FROM AUTHOR]