Photocatalysis has high potential in the cleavage of Cβ-O bond in lignin into high-value aromatic monomers; however, the inefficient Cα-H bond activation in lignin and a low hydrogen transfer efficiency on the photocatalyst's surfaces have limited its application in photocatalytic lignin conversion. This study indicates that the cleavage of the Cβ-O bond can be improved by the generation of the Cα radical intermediate through Cα-H bond activation, and the formation of desirable aromatic products can be significantly improved by the enhanced hydrogen transfer efficiency from photocatalyst surfaces to aromatic monomeric radicals. We elaborately designed the half-unit-cell MoS2/ZnIn2S4 monolayer with a thickness of ∼1.7 nm to promote the hydrogen transfer efficiency on the photocatalyst surfaces. The ultrathin structure can shorten the diffusion distance of charge carriers from the interior to the surfaces and tight interface between MoS2 and ZnIn2S4 to facilitate the migration of photogenerated electrons from ZnIn2S4 to MoS2, therefore improving the selectivity of desirable products. The adsorbed hydroxyl radical (*OH) on the surfaces of MoS2/ZnIn2S4 from water oxidation can significantly reduce the bond dissociation energy (BDE) of Cα-H bond in PP-ol from 2.38 to 1.87 eV, therefore improving the Cα-H bond activation. The isotopic experiments of H2O/D2O indicate that the efficiency of *OH generation is an important step in Cα-H bond activation for PP-ol conversion to aromatic monomers. In summary, PP-ol can completely convert to 86.6% phenol and 82.3% acetophenone after 1 h of visible light irradiation by using 3% MoS2/ZnIn2S4 and the assistance of *OH, which shows the highest conversion rate compared to previous works.
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