Photocatalytic Depolymerization of Lignin: C-O Bond Cleavage in β-O-4 Models Using S-Doped Ultra-Thin Bi3O4Cl Nanosheets

The selective depolymerization of β-O-4 lignin models into high-value aromatic monomers using photocatalysis presents both significant opportunities and challenges. Photocatalysts often face issues such as high photogenerated carrier recombination rates and limited operational lifetimes. This study introduces S doping to modulate the surface interface of Bi₃O₄Cl (BOC) nanosheets, enhancing C-O bond cleavage efficiency in β-O-4 lignin models under visible light at ambient temperatures. Comprehensive characterization, including atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), and density functional theory (DFT) analysis, revealed that S doping reduces BOC nanosheet thickness to 1.51 nm and promotes charge carrier separation, thereby generating greater concentrations of reactive species, specifically •O₂^- and •OH. Photocatalytic depolymerization experiments demonstrated that S-doped BOC achieved a C-O bond cleavage selectivity of 93% and an aromatic monomer yield of 629.03 μmol/g/h (i.e., 1.5 times higher than that of undoped BOC). This work provides a strategic approach to designing photocatalysts with enhanced selectivity and efficiency for lignin depolymerization.