Abstract
Developing multifunctional photocatalysts is promising for selective and tunable lignin conversion to valuable chemicals. Herein, recyclable TCP photocatalysts with acidic, basic, and redox sites were developed by integrating {001} facet-containing TiO2, Cu, and polyoxometalates P2W17V together. Lignin model compound with β-O-4 structure was effectively and adjustably transformed to aromatic aldehydes and phenol in photocatalysis, involving Cβ-centered radical-mediated Cα-Cβ bond cleavage and elimination-hydrolysis-induced Cβ-O bond cleavage. Cα-Cβ bond scission selectivity exceeded 90 % by prolonging reaction time, whereas Cβ-O bond breakage was pronounced at short reaction time. Cu interacted with reacting species, improved charge transfer, and promoted Cβ-O bond scission. P2W17V acted as acidic-basic-redox components, accelerated electron acceptance, and facilitated Cα-Cβ bond cleavage. Additionally, alkaline lignin could also be photocatalyzed to vanillin. This work presents the first instance of Cα-Cβ/Cβ-O bond breakage modulation by varying reaction time. The design of trifunctional photocatalyst provides a new way for deriving valuable products from lignin.
Published Version
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