Controlling reaction pathways via selective C-O activation for highly efficient biomass oriented-upgrading.

• Highly dispersed and stable Cu nanoparticles was finely encapsulated in HZSM-5. • Selectivity of valeric biofuel from GVL upgrading was preciously controlled. • Synergetic effect of confined Cu centers and acidic zeolite was crucial for the catalytic performance. • C-O bond activation mode was determined by distinct electrons redistributions on GVL in different adsorbed environments. Achieving precise selectivity control by driving specific reaction paths involving selective C-O bond activation of multifunctional molecules in renewable biomass oriented-upgrading is highly attractive but challenging. Herein, a facile in-situ hydrothermal strategy was developed to obtain highly dispersed and stable Cu nanoparticles encapsulated in well-organized HZSM-5 zeolite, which exhibited extraordinary selectivity control in the lignocellulosic biomass-derived γ-valerolactone (GVL) upgrading toward valuable valeric biofuels with good stability. The as-synthesized Cu@HZSM-5 exhibited a framework Al-dependent Cu distribution characteristic in HZSM-5, while the Cu spatial confinement by zeolite framework together with the synergetic effect of confined Cu centers and acidic zeolite support endowed the optimized Cu@HZSM-5 catalysts exceedingly high hydro-conversion efficiency. Theoretical calculations demonstrated that the transferred electrons from Cu to GVL in different zeolite microenvironments (zeolite-encapsulated and -impregnated structure) showed the very distinct redistributions on the C atoms of GVL, which was crucial to tune the ring C-O bond activation mode in GVL ring-opening, consequently giving a well-controlled product selectivity. [ABSTRACT FROM AUTHOR]