Hydrodeoxygenation represents a promising route for upgrading lignin-derived bio-oil into value-added fine chemicals,but it is challenging to obtain high yield and selectivity due to the varying dissociation energy of...Hydrodeoxygenation represents a promising route for upgrading lignin-derived bio-oil into value-added fine chemicals,but it is challenging to obtain high yield and selectivity due to the varying dissociation energy of different oxygen-containing functional groups.Here,we strategically engineered a robust Cu-based catalyst for catalyzing vanillin to 4-methylguaiacol in a H-donor solvent under an inert N_(2) atmosphere,achieving simultaneously>99.9%conversion and near-theoretical selectivity(99.6%),as well as excellent cycling durability.First-principles calculations and control catalytic experiments confirmed the enhanced performance originated from(i)the downshifted d-band center of in situ generated Cu^(0) species induced by Al Lewis acid sites and(ii)the synergistic interplay between these Cu^(0) centers and adjacent Al Lewis acid sites,facilitated by isopropanol-mediated hydrogen transfer.This study demonstrates the feasibility of rationally designing high-performance catalysts featuring synergistic nonnoble metals with Lewis acid sites,enabling efficient and selective upgrade of renewable peroxidized compounds into value-added products with enhanced cost-effectiveness and process safety.展开更多
基金supported by the National Natural Science Foundation of China(No.22278047,No.22208038,No.22508030,and No.22208040)Fundamental Research Funds for the Universities of Liaoning Province(No.LJ212410152038,No.LJBKY2025057No.2025-BS-0463)。
文摘Hydrodeoxygenation represents a promising route for upgrading lignin-derived bio-oil into value-added fine chemicals,but it is challenging to obtain high yield and selectivity due to the varying dissociation energy of different oxygen-containing functional groups.Here,we strategically engineered a robust Cu-based catalyst for catalyzing vanillin to 4-methylguaiacol in a H-donor solvent under an inert N_(2) atmosphere,achieving simultaneously>99.9%conversion and near-theoretical selectivity(99.6%),as well as excellent cycling durability.First-principles calculations and control catalytic experiments confirmed the enhanced performance originated from(i)the downshifted d-band center of in situ generated Cu^(0) species induced by Al Lewis acid sites and(ii)the synergistic interplay between these Cu^(0) centers and adjacent Al Lewis acid sites,facilitated by isopropanol-mediated hydrogen transfer.This study demonstrates the feasibility of rationally designing high-performance catalysts featuring synergistic nonnoble metals with Lewis acid sites,enabling efficient and selective upgrade of renewable peroxidized compounds into value-added products with enhanced cost-effectiveness and process safety.
