Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework



Zheng, Jian, Ye, Jingyun, Ortuno, Manuel A, Fulton, John L, Gutierrez, Oliver Y, Camaioni, Donald M, Motkuri, Radha Kishan, Li, Zhanyong, Webber, Thomas E, Mehdi, B Layla ORCID: 0000-0002-8281-9524
et al (show 7 more authors) (2019) Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 141 (23). pp. 9292-9304.

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Abstract

Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal-organic framework (MOF) via cation exchange and subsequent oxidation at 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol at 150-200 °C. At 150 °C and 1 bar methane, approximately a third of the copper centers are involved in converting methane to methanol. Methanol productivity increased by 3-4-fold and selectivity increased from 70% to 90% by increasing the methane pressure from 1 to 40 bar. Density functional theory showed that reaction pathways on various copper sites are able to convert methane to methanol, the copper oxyl sites with much lower free energies of activation. Combining studies of the stoichiometric activity with characterization by in situ X-ray absorption spectroscopy and density functional theory, we conclude that dehydrated dinuclear copper oxyl sites formed after activation at 200 °C are responsible for the activity.

Item Type: Article
Depositing User: Symplectic Admin
Date Deposited: 29 Aug 2019 09:59
Last Modified: 19 Jan 2023 00:37
DOI: 10.1021/jacs.9b02902
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3049553