Visible-Light-Driven Self-Hydrogen Transfer Hydrogenolysis of Lignin Models and Extracts into Phenolic Products

Obtaining high selectivity of aromatic monomers from renewable lignin has been extensively pursued but is still unsuccessful, hampered by the need to efficiently cleave C-O/C-C bonds and inhibit lignin proliferation reactions. Herein, we report a transfer hydrogenolysis protocol using a heterogeneous ZnIn2S4 catalyst driven by visible light. In this process, alcoholic groups (C alpha H-OH) of lignin act as hydrogen donors. Proliferation of phenolic products to dark substances is suppressed under visible light illumination at low temperature (below 50 degrees C); formation of a light and transparent reaction solution allows visible light to be absorbed by the catalyst. With this strategy, 71-91% yields of phenols in the conversion of lignin beta-O-4 models and a 10% yield of p-hydroxyl acetophenone derivatives from organosolv lignin are achieved. Mechanistic studies reveal that C alpha H-OH groups of lignin beta-O-4 linkage are initially dehydrogenated on ZnIn2S4 to form a hydrogen pool, and the adjacent C-beta-O bond is subsequently hydrogenolytically cleaved to two monomers by the hydrogen pool. Thus, the dehydrogenation and hydrogenolysis reaction are integrated in one-pot with lignin itself as a hydrogen donor. This study shows a promising way of supplying phenolic compounds by taking advantages of both renewable biomass feedstocks and photoenergy.