Depolymerization of Native Lignin over Thiol Capped Ultrathin ZnInS Microbelts Mediated by Photogenerated Thiyl Radical.

The valorization of native lignin to functionalized aromatic compounds under visible light is appealing yet challenging. In this communication, colloidal mercaptoalkanoic acid capped ultrathin ZnInS (ZIS) microbelts was successfully fabricated, which was used as a superior catalyst for depolymerization of native lignin in birch woodmeal under visible light, with an optimum yield of 28.8 wt % to functionalized aromatic monomers achieved in 8 h. The capped mercaptoalkanoic acid not only enables a solvent modulated reversible interchange of ZIS between the colloidal state for efficient reaction and the aggregated state for facile separation, but also serves as a precursor for light initiated generation of reactive thiyl radical for highly selective cleavage of β-O-4 bond in native lignin. This work provides a green and efficient strategy for the depolymerization of native lignin to functionalized aromatic monomers under mild conditions, which involves a new mechanism for the cleavage of β-O-4 bonds in native lignin. The capability of cleavage of β-O-4 bonds in native lignin by photogenerated thiyl radicals also demonstrates the great potential of using photogenerated thiyl radicals in organics transformations.