Selective
Methane Oxidation to Methanol on Cu-Oxo
Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic
Framework
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. Lercher
10.1021/jacs.9b02902.s001
https://acs.figshare.com/articles/journal_contribution/Selective_Methane_Oxidation_to_Methanol_on_Cu-Oxo_Dimers_Stabilized_by_Zirconia_Nodes_of_an_NU-1000_Metal_Organic_Framework/8210795
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 <i>in situ</i> 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.
2019-05-22 00:00:00
cation exchange
copper oxyl sites
X-ray absorption spectroscopy
dinuclear copper oxyl sites
Selective Methane Oxidation
Copper-exchanged MOFs
dinuclear copper species
Zirconia Nodes
stoichiometric activity
reaction pathways
NU
methane pressure
activation
copper sites
40 bar
1 bar methane
Cu-Oxo Dimers Stabilized
-1000
methanol
Methanol productivity
copper centers