Hierarchical Porous Metal–Organic Polyhedra for Efficient Oxidative Cleavage of β-O-4 Bonds in Lignin Model Compound
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.
Authors
- Alena M. Sheveleva (ORCID: https://orcid.org/0000-0001-6190-5944)
- Emma K. Gibson (ORCID: https://orcid.org/0000-0002-7839-3786)
- Shaojun Xu (ORCID: https://orcid.org/0000-0002-8026-8714)
- Xinchen Kang (ORCID: https://orcid.org/0000-0003-0593-0840)
- C. Richard A. Catlow (ORCID: https://orcid.org/0000-0002-1341-1541)
- Sihai Yang⧫ (ORCID: https://orcid.org/0000-0002-1111-9272)
- Floriana Tuna (ORCID: https://orcid.org/0000-0002-5541-1750)
- Eric J. L. McInnes (ORCID: https://orcid.org/0000-0002-4090-7040)
- Lifei Liu
- Lili Li
- Kai Lyu (ORCID: https://orcid.org/0000-0002-1714-3716)
- Martin Schröder (ORCID: https://orcid.org/0000-0001-6992-0700)
- Joseph H. Carter (ORCID: https://orcid.org/0000-0001-5530-7390)
- Chiu C. Tang (ORCID: https://orcid.org/0000-0001-8721-7920)
- Yinlin Chen (ORCID: https://orcid.org/0000-0001-7878-2063)
- Zi Wang (ORCID: https://orcid.org/0000-0003-3197-2550)
- Tian Luo (ORCID: https://orcid.org/0000-0002-5788-5060)
- Xue Han (ORCID: https://orcid.org/0000-0002-2190-9227)
- Hengan Wang
- Buxing Han (ORCID: https://orcid.org/0000-0003-0440-809X)
Institutions
- Peking University (CN)
- Beijing Normal University (CN)
- Diamond Light Source (GB)
- University of Manchester (GB)
- Research Complex at Harwell (GB)
- Beijing National Laboratory for Molecular Sciences (CN)
- University College London (GB)
- University of Glasgow (GB)
- Cardiff University (GB)
Publication Details
- Journal
- CCS Chemistry
- Published
- 2024-12-20
- DOI
- https://doi.org/10.31635/ccschem.024.202404991
- Citations
- 3
- Primary Topic
- Oxidative Organic Chemistry Reactions
- Type
- article
- Field-Weighted Citation Impact
- 0.75
Funders
- Engineering and Physical Sciences Research Council