Photocatalytic Oxidation–Hydrogenolysis of Lignin β‑O‑4 Models via a Dual Light Wavelength Switching Strategy

One of the challenges of depolymerizing lignin to valuable aromatics lies in the selective cleavage of the abundant C–O bonds of β-O-4 linkages. Herein we report a photocatalytic oxidation–hydrogenolysis tandem method for cleaving C–O bonds of β-O-4 alcohols. The Pd/ZnIn₂S₄ catalyst is used in the aerobic oxidation of α-C–OH of β-O-4 alcohols to α-CO with 455 nm light, and then a TiO₂–NaOAc system is employed for cleaving C–O bonds neighboring the α-CO bonds through a hydrogenolysis reaction by switching to 365 nm light. Interestingly, the oxidation–hydrogenolysis tandem reaction can be conducted in one pot to offer ketones and phenols (up to 90% selectivity) via a dual light wavelength switching (DLWS) strategy. EPR and metal loading experiments elucidate that Ti³⁺ in TiO₂ is formed in situ and is responsible for the photocatalytic hydrogenolysis through electron transfer from Ti³⁺ to the β-O-4 ketones.