Remote allosteric control of single-atom Cu sites in Zr-MOFs enables selective CH ₄ hydroxylation
8 affiliations
- 1CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
- 2Univ. Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 – UCCS – Unité de Catalyse et Chimie du Solide, Lille F-59000, France.
- 3State Key Laboratory of Chemistry for NBC Hazards Protection, College of Chemistry, Fuzhou University, Fuzhou 350116, China.
- 4Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
- 5State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, China.
- 6University of Chinese Academy of Sciences, Beijing 100049, China.
- 7Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, 215123, China.
- 8Institut Michel-Eugène Chevreul, Villeneuve-d’Ascq 59655, France.
Abstract
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.
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BibTeX
@article{fang2026remote,
title = {{Remote allosteric control of single-atom Cu sites in Zr-MOFs enables selective CH ₄ hydroxylation}},
author = {Geqian Fang and Fenfei Wei and Wenjun Yu and Yu Kang and Maya Marinova and Lulu Chen and Lin Li and Vitaly V. Ordomsky and Anne-Marie Blanchenet and Sen Lin and Jian Lin and Xiaodong Wang and Xianzhi Fu and Andrei Y. Khodakov and Tao Zhang},
journal = {Science Advances},
year = {2026},
month = oct,
doi = {10.1126/sciadv.aei9401},
url = {https://www.science.org/doi/10.1126/sciadv.aei9401},
note = {CC BY},
}
RIS
TY - JOUR
TI - Remote allosteric control of single-atom Cu sites in Zr-MOFs enables selective CH ₄ hydroxylation
AU - Geqian Fang
AU - Fenfei Wei
AU - Wenjun Yu
AU - Yu Kang
AU - Maya Marinova
AU - Lulu Chen
AU - Lin Li
AU - Vitaly V. Ordomsky
AU - Anne-Marie Blanchenet
AU - Sen Lin
AU - Jian Lin
AU - Xiaodong Wang
AU - Xianzhi Fu
AU - Andrei Y. Khodakov
AU - Tao Zhang
PY - 2026
DA - 2026/10/16
JO - Science Advances
DO - 10.1126/sciadv.aei9401
UR - https://www.science.org/doi/10.1126/sciadv.aei9401
AB - 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.
SN - 2375-2548
ER -