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Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework
journal contribution
posted on 2019-05-22, 00:00 authored by Jian Zheng, Jingyun Ye, Manuel A. Ortuño, John L. Fulton, Oliver Y. Gutiérrez, Donald M. Camaioni, Radha Kishan Motkuri, Zhanyong Li, Thomas E. Webber, B. Layla Mehdi, Nigel D. Browning, R. Lee Penn, Omar K. Farha, Joseph T. Hupp, Donald G. Truhlar, Christopher J. Cramer, Johannes A. LercherMononuclear 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.
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cation exchangecopper oxyl sitesX-ray absorption spectroscopydinuclear copper oxyl sitesSelective Methane OxidationCopper-exchanged MOFsdinuclear copper speciesZirconia Nodesstoichiometric activityreaction pathwaysNUmethane pressureactivationcopper sites40 bar1 bar methaneCu-Oxo Dimers Stabilized-1000methanolMethanol productivitycopper centers
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