Selective Photocatalytic C–C Bond Cleavage of Lignin Models and Conversion to High-Value Chemical by Polyoxometalate Under a Mild Water-Based Environment

Abstract

Selective bond cleavage using a photoredox reaction is a powerful technique in the chemical conversion of biomass such as lignin since it enables us to produce value-added aromatic compounds by controlling the activation of certain chemical bonds. Also, a water-based environment would be preferred for the sake of an eco-friendly reaction, additionally having the advantage of utilizing water-originated species such as •OH and H2O2. However, a direct cleavage of the C–C bond is still challenging due to the difficulties in tailoring redox potentials of catalysts relevant to covalent bond decoupling. Herein, we investigate a selective C–C bond cleavage of the β-O-4 lignin model compound using giant Keplerate polyoxometalates as photocatalysts. The redox potentials of photocatalysts are varied by changing metal compositions, and the correlation between redox potential and covalent bond decoupling is elucidated, probing each set of active radicals by HOMO and LUMOs. Especially, Mo132 shows a highly selective C–C bond cleavage with hydroxyl groups in the lignin model and produces phenyl formate─a effective CO surrogate for the synthesis of various organic compounds─as the main product (97.8% of product selectivity) in a water-based condition. Furthermore, Mo132 decomposes other aromatic polymer models, indicating the potential of photocatalytic C–C bond decoupling of polymers under a benign environment.