Hierarchical porous metal–organic polyhedra for efficient oxidative cleavage of β-o-4 bonds in lignin model compound

Kang, Xinchen, Li, Lili, Wang, Hengan, Luo, Tian, Xu, Shaojun, Chen, Yinlin, Carter, Joseph H., Wang, Zi, Sheveleva, Alena M., Lyu, Kai, Han, Xue, Tuna, Floriana, McInnes, Eric J. L., Tang, Chiu C., Liu, Lifei, Han, Buxing, Gibson, Emma K., Catlow, C. Richard A. ORCID: https://orcid.org/0000-0002-1341-1541, Yang, Sihai and Schröder, Martin 2025. Hierarchical porous metal–organic polyhedra for efficient oxidative cleavage of β-o-4 bonds in lignin model compound. CCS Chemistry 10.31635/ccschem.024.202404991

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Abstract

Catalytic cleavage of β-O-4 linkages is an essential but challenging step in the depolymerization of lignin. Here, we report the templated electrosynthesis of a hydrophobic metal–organic polyhedral catalyst (Cu-MOP-e), which exhibits excellent hydrothermal stability and exceptional activity for this reaction. The oxidative cleavage of 2-phenoxyacetophenone, 1, a lignin model compound, over Cu-MOP-e at 90 °C for 1 h affords full conversion with yields of the monomer products phenol and benzoic acid of 99%. The reusability of Cu-MOP-e was confirmed by carrying out ten cycles of reaction. The mechanism of catalyst-substrate binding was investigated by high-resolution synchrotron X-ray powder diffraction, in situ X-ray absorption spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory (DFT) calculations. The combination of optimal porosity and active Cu(II) sites provides confined binding of 2-phenoxyacetophenone, thus promoting the cleavage of β-O-4 linkage under relatively mild conditions.

Item Type:	Article
Date Type:	Published Online
Status:	In Press
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	Chinese Chemical Society
ISSN:	2096-5745
Date of First Compliant Deposit:	6 February 2025
Date of Acceptance:	6 December 2024
Last Modified:	06 Feb 2025 10:00
URI:	https://orca.cardiff.ac.uk/id/eprint/175990

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