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.
| Original language | English |
|---|---|
| Pages (from-to) | 9292-9304 |
| Number of pages | 13 |
| Journal | Journal of the American Chemical Society |
| Volume | 141 |
| Issue number | 23 |
| DOIs | |
| Publication status | Published - Jun 12 2019 |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework. / Zheng, Jian; Ye, Jingyun; Ortuño, Manuel A.; Fulton, John L.; Gutiérrez, Oliver Y.; Camaioni, Donald M.; Motkuri, Radha Kishan; Li, Zhanyong; Webber, Thomas E.; Mehdi, B. Layla; Browning, Nigel D.; Penn, R. Lee; Farha, Omar K.; Hupp, Joseph T; Truhlar, Donald G.; Cramer, Christopher J.; Lercher, Johannes A.
In: Journal of the American Chemical Society, Vol. 141, No. 23, 12.06.2019, p. 9292-9304.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework
AU - Zheng, Jian
AU - Ye, Jingyun
AU - Ortuño, Manuel A.
AU - Fulton, John L.
AU - Gutiérrez, Oliver Y.
AU - Camaioni, Donald M.
AU - Motkuri, Radha Kishan
AU - Li, Zhanyong
AU - Webber, Thomas E.
AU - Mehdi, B. Layla
AU - Browning, Nigel D.
AU - Penn, R. Lee
AU - Farha, Omar K.
AU - Hupp, Joseph T
AU - Truhlar, Donald G.
AU - Cramer, Christopher J.
AU - Lercher, Johannes A.
PY - 2019/6/12
Y1 - 2019/6/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85067056484&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85067056484&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b02902
DO - 10.1021/jacs.9b02902
M3 - Article
C2 - 31117650
AN - SCOPUS:85067056484
VL - 141
SP - 9292
EP - 9304
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 23
ER -