Unlocking Structure–Reactivity Relationships for Catalytic Hydrogenolysis of Lignin into Phenolic Monomers

Abstract Lignin depolymerization into aromatic monomers with high yields and selectivity is essential for the economic feasibility of biorefinery. However, the relationship between lignin structure and its reactivity for upgradeability is still poorly understood, in large part owing to the difficulty in quantitative characterization of lignin structural properties. To overcome these shortcomings, advanced NMR technologies [2D HSQC (heteronuclear single quantum coherence) and 31 P] were used to accurately quantify lignin functionalities. Diverse lignin samples prepared from Eucalyptus grandis with varying β‐O‐4 linkages were subjected to Pd/C‐catalyzed hydrogenolysis for efficient C−O bond cleavage to achieve theoretical monomer yields. Strong correlations were observed between the yield of monomeric aromatic compounds and the structural features of lignin, including the contents of β‐O‐4 linkages and phenolic hydroxyl groups. Notably, a combined yield of up to 44.1 wt % was obtained from β‐aryl ether rich in native lignin, whereas much lower yields were obtained from technical lignins low in β‐aryl ether content. This work quantitatively demonstrates that the lignin reactivity for acquiring aromatic monomer yields varies depending on the lignin fractionation processes.