Issue 29, 2025

Selective C–O bond cleavage enhances aromatics production from lignin-derived platform molecules with ethanol as a hydrogen donor

Abstract

Selective catalytic cleavage of C–O bonds during the hydrodeoxygenation (HDO) of lignin-derived phenolics is essential for producing renewable aromatics from biomass. The HDO process typically involves the use of high-pressure molecular hydrogen, which poses safety concerns and lacks sustainability. Herein, we report an effective catalytic approach that integrates the aqueous-phase reforming (APR) of ethanol with the selective HDO of lignin-derived phenol to benzene over a well-defined Pt/Al2O3 catalyst. The effects of catalyst support, ethanol-to-water ratios, and reaction temperatures on in situ HDO processes were systematically explored and thoroughly discussed. The competitive routes of C–O bond hydrogenolysis and benzene ring hydrogenation during HDO of phenol were found to be significantly dependent on the H2 produced by the APR of ethanol and variations in reaction parameters. A lower H2 pressure, generated from an optimized Vethanol/Vwater of 3 : 5 and a high reaction temperature of 280 °C, favored the selective cleavage of C–O bonds rather than the hydrogenation of benzene rings, resulting in a relatively high phenol conversion of ca. 57% with a benzene selectivity of ca. 97% after 2 h of reaction. The proposed reaction pathways involved in the currently developed in situ HDO process provided a deep understanding of the pronounced selectivity towards benzene formation from phenol under optimized reaction conditions. The conversion of other representative lignin-derived phenolics and ethers further validated the superiority and versatility of the developed catalytic system in producing aromatic compounds from lignin biomass.

Graphical abstract: Selective C–O bond cleavage enhances aromatics production from lignin-derived platform molecules with ethanol as a hydrogen donor

Supplementary files

Article information

Article type
Paper
Submitted
27 Apr 2025
Accepted
26 Jun 2025
First published
03 Jul 2025

Green Chem., 2025,27, 8959-8971

Selective C–O bond cleavage enhances aromatics production from lignin-derived platform molecules with ethanol as a hydrogen donor

H. Zhang, Q. Yi, H. Geng, Z. Liu, W. Luo, Z. Wang and Y. Liu, Green Chem., 2025, 27, 8959 DOI: 10.1039/D5GC02104A

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