Photocatalytic Oxidation–Hydrogenolysis of Lignin β‑O‑4 Models via a Dual Light Wavelength Switching Strategy
journal contributionposted on 2016-10-06, 00:00 authored by Nengchao Luo, Min Wang, Hongji Li, Jian Zhang, Huifang Liu, Feng Wang
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-CO with 455 nm light, and then a TiO2–NaOAc system is employed for cleaving C–O bonds neighboring the α-CO 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.
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EPRDLWShydrogenolysis reactioncleavingbondoffer ketonesβ- O -4 linkagesoxidationelectron transferdepolymerizing ligninα-365 nm lighttandemphotocatalytic hydrogenolysismetal loading experiments elucidateDual Light Wavelength Switching StrategyTiO 2light wavelengthβ- O -4 alcoholsβ- O -4 ketones455 nm light