Efficient Photocatalytic Cleavage of Lignin Models by a Soluble Perylene Diimide/Carbon Nitride S‐Scheme Heterojunction

3,4,9,10-Perylenetetracarboxylic dianhydride (PDI) is one of the best n-type organic semiconductors and an ideal light-driven catalyst for lignin depolymerization. However, the charge localization effect and the excessively strong intermolecular aggregation trend in PDI result in rapid electron-hole (e⁻ -h⁺ ) recombination, which limits photocatalytic performance. Herein, polymeric carbon nitride/polyhedral oligomeric silsesquioxane PDI (p-CN/P-PDI) S-scheme heterojunction photocatalyst was prepared by the solvent evaporation-deposition method for C-C bond selective cleavage of lignin β-O-4 model. Based on the material characterization results, the synergic role of polyhedral oligomeric silsesquioxane (POSS) and S-scheme heterojunction maintains appropriate aggregation domains, achieves better solar light utilization, faster charge-transfer efficiency, and greater redox capacity. Notably, the 3 % p-CN/P-PDI heterostructure exhibits a remarkable enhancement in cleavage conversion efficiency, achieving approximately 16.42 and 2.57 times higher conversion rates compared to polyhedral oligomeric silsesquioxane modified PDI (POSS-PDI) and polymeric carbon nitride (p-CN), respectively.