Efficient Selective Cleavage of C−C Bonds in Lignin under Visible Light Enabled by the Fe-doped Mesoporous Graphitic Carbon Nitride Photocatalyst
Industrial Crops and Products（2024）
Institute of Chemical Industry of Forestry Products
Abstract
Despite the promise of photocatalysis for extracting aromatic compounds from renewable lignin feedstocks, the selective cleavage of C alpha-C beta bonds in lignin under mild conditions poses a persistent challenge, primarily due to their elevated dissociation energies and steric hindrance. Herein, an efficient photocatalytic strategy for selectively breaking the C alpha-C beta bonds of lignin with visible-light irradiation and room temperature is proposed, facilitated by the Zn(II)-doped porous graphitic carbon nitride (Zn/CN) photocatalyst. Reduced energy band gap and photoluminescence, along with intensified visible-light absorption and enhanced photocurrent of Zn/CN, contribute to its efficacy in photocatalytic activity. Consequently, the lignin model compound (2-phenoxy-1phenylethanol) achieves a conversion rate of 99 %, demonstrating a notable selectivity of 97 % in specifically breaking the C alpha-C beta bonds. Mechanistic investigations identify that photogenerated holes play a pivotal role during the photocatalytic conversion. Additionally, the activity and selectivity of Zn/CN photocatalyst are further confirmed by the successful photocatalytic conversion of pine kraft lignin, yielding high-value chemicals such as benzoic acid and vanillin. This research proposes an economical, efficient, and facile method for utilizing renewable lignin feedstocks under photocatalysis, thus advancing the production of high-value aromatic compounds.
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Key words
Photocatalyst,Visible-light,Lignin depolymerization,Selective cleavage
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