Remote allosteric control of single-atom Cu sites in Zr-MOFs enables selective CH 4 hydroxylation
Highly selective oxidation of methane to liquid oxygenates under mild conditions remains challenging because of the difficulty in controlling overoxidation at highly reactive sites. Here, we demonstrate remote control of single-atom Cu reactivity through outer-shell coordination engineering in Zr-based metal-organic frameworks (MOFs). By anchoring Cu 1 to Zr-oxo nodes in UiO-66-X (X = -NO 2 , -H, and -CH 3 ), remote X-BDC ligands systematically modulate the electronic properties of Cu 1 sites and the catalytic microenvironment. In situ characterization combined with ab initio molecular dynamics in an explicitly solvated aqueous environment reveals a dynamic outer-shell-to-inner-shell regulation that reshapes the active structure and reactive oxygen species around Cu 1 sites, thereby facilitating CH 4 activation. In particular, the electron-withdrawing NO 2 -BDC ligand creates electron-deficient Cu 1 - • OH* sites, while adsorbed water further regulates active-site conformation. Consequently, Cu 1 /U6-NO 2 achieves a turnover frequency of 322.4 h −1 with nearly 100% oxygenate selectivity under mild conditions, establishing a general strategy for overcoming activity-selectivity trade-offs in methane conversion.
Authors
- Yu Seon Kang (ORCID: https://orcid.org/0000-0003-0336-454X)
- Maya Marinova (ORCID: https://orcid.org/0000-0001-8635-0973)
- Sen Lin (ORCID: https://orcid.org/0000-0002-2288-5415)
- Fenfei Wei (ORCID: https://orcid.org/0000-0003-1264-3372)
- Anne-Marie Blanchenet (ORCID: https://orcid.org/0000-0003-1183-904X)
- Andreï Y. Khodakov (ORCID: https://orcid.org/0000-0003-4599-3969)
- Geqian Fang (ORCID: https://orcid.org/0009-0008-3846-7403)
- Vitaly V. Ordomsky (ORCID: https://orcid.org/0000-0002-4814-5052)
- Tao Zhang (ORCID: https://orcid.org/0000-0001-9470-7215)
- Xiaodong Wang (ORCID: https://orcid.org/0000-0002-8705-1278)
- Jian Lin (ORCID: https://orcid.org/0000-0002-1084-7446)
- Lulu Chen (ORCID: https://orcid.org/0009-0006-9962-5984)
- W K Yu (ORCID: https://orcid.org/0009-0001-3466-9197)
- Lin Li
- Xianzhi Fu
Institutions
- Centre National de la Recherche Scientifique (FR)
- Dalian Institute of Chemical Physics (CN)
- Chinese Academy of Sciences (CN)
- Université de Lille (FR)
- Suzhou Institute of Nano-tech and Nano-bionics (CN)
- Unité de catalyse et de chimie du solide de Lille (FR)
- University of Chinese Academy of Sciences (CN)
- Institut Michel-Eugène Chevreul (FR)
- École Centrale de Lille (FR)
- Fuzhou University (CN)
- Nanjing University (CN)
Publication Details
- Journal
- Science Advances
- Published
- 2026-10-14
- DOI
- https://doi.org/10.1126/sciadv.aei9401
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Agence Nationale de la Recherche
- National Natural Science Foundation of China
- Youth Innovation Promotion Association of the Chinese Academy of Sciences
- Association Neurofibromatoses et Recklinghause
- European Regional Development Fund
- Science Fund for Distinguished Young Scholars of Dalian Province
- National Supercomputing Center, Korea Institute of Science and Technology Information
- Dalian National Laboratory for Clean Energy