Metal-Acid Synergy: Hydrodeoxygenation of Anisole over Pt/Al-SBA-15

Hydrodeoxygenation (HDO) is a promising technology to upgrade fast pyrolysis bio-oils but it requires active and selective catalysts. Here we explore the synergy between the metal and acid sites in the HDO of anisole, a model pyrolysis bio-oil compound, over mono- and bi-functional Pt/(Al)-SBA-15 catalysts. Ring hydrogenation of anisole to methoxycyclohexane occurs over metal sites and is structure sensitive; it is favored over small (4 nm) Pt nanoparticles, which confer a turnover frequency (TOF) of approximately 2000 h^-1 and a methoxycyclohexane selectivity of approximately 90 % at 200 °C and 20 bar H₂ ; in contrast, the formation of benzene and the desired cyclohexane product appears to be structure insensitive. The introduction of acidity to the SBA-15 support promotes the demethyoxylation of the methoxycyclohexane intermediate, which increases the selectivity to cyclohexane from 15 to 92 % and the cyclohexane productivity by two orders of magnitude (from 15 to 6500 mmol g_Pt ^-1  h^-1 ). Optimization of the metal-acid synergy confers an 865-fold increase in the cyclohexane production per gram of Pt and a 28-fold reduction in precious metal loading. These findings demonstrate that tuning the metal-acid synergy provides a strategy to direct complex catalytic reaction networks and minimize precious metal use in the production of bio-fuels.