Visible light-driven selective cleavage of Cα-Cβ or Cβ-O bond in lignin β-O-4 model into high-value aromatic chemicals over surface modified 2D g-C3N4

Abstract

Selective cleavage of C–C/C–O linkages in lignin is highly pursued to obtain aromatic monomers but remains challenging due to distinct dissociation energies and steric hindrance. Herein, two photocatalysts were reported to respectively scissor the Cα-Cβ and Cβ-O in lignin β-O-4 model (2-phenoxy-1-phenylethanol) based on the reactive oxygen species control. On one hand, 2D g-C3N4 promotes protons extraction from Cβ-H and ·O2– formation, which further scissored Cα-Cβ via six-membered ring transition state produced via the coupling of ·Cβ and ·HO2, providing aromatic aldehydes and esters. When single-atomic Cu+ species were coordinated with N atoms in 2D g-C3N4 during surface modification, however, the ·O2– formation was prohibited because of the improper redox potentials. Under the catalysis of Cu/2D g-C3N4, CαO-H would be preferentially activated, causing the selective Cβ-O cleavage via self-hydrogen transfer hydrogenolysis to provide phenolics and aromatic ketones. The access and inhibition mechanism for ·O2– formation as well as the different catalytic mechanisms for two reaction pathways were discussed. Current work shows a promising way to selectively supply aromatic chemicals using the renewable biomass and photoenergy.