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

Research output: Contribution to journalArticle

2 Citations (Scopus)

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 languageEnglish
Pages (from-to)9292-9304
Number of pages13
JournalJournal of the American Chemical Society
Volume141
Issue number23
DOIs
Publication statusPublished - Jun 12 2019

Fingerprint

Methane
Zirconia
Dimers
Methanol
Copper
Metals
Oxidation
Density functional theory
X-Ray Absorption Spectroscopy
Chemical activation
X ray absorption spectroscopy
Free energy
zirconium oxide
Cations
Ion exchange
Productivity
Positive ions
Oxygen
Pressure

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Zheng, J., Ye, J., Ortuño, M. A., Fulton, J. L., Gutiérrez, O. Y., Camaioni, D. M., ... Lercher, J. A. (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), 9292-9304. https://doi.org/10.1021/jacs.9b02902

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 journalArticle

Zheng, J, Ye, J, Ortuño, MA, Fulton, JL, Gutiérrez, OY, Camaioni, DM, Motkuri, RK, Li, Z, Webber, TE, Mehdi, BL, Browning, ND, Penn, RL, Farha, OK, Hupp, JT, Truhlar, DG, Cramer, CJ & Lercher, JA 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, vol. 141, no. 23, pp. 9292-9304. https://doi.org/10.1021/jacs.9b02902
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. / Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 23. pp. 9292-9304.
@article{a8d8543e1c1046a1923ae49962ab2fa6,
title = "Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal-Organic Framework",
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.",
author = "Jian Zheng and Jingyun Ye and Ortu{\~n}o, {Manuel A.} and Fulton, {John L.} and Guti{\'e}rrez, {Oliver Y.} and Camaioni, {Donald M.} and Motkuri, {Radha Kishan} and Zhanyong Li and Webber, {Thomas E.} and Mehdi, {B. Layla} and Browning, {Nigel D.} and Penn, {R. Lee} and Farha, {Omar K.} and Hupp, {Joseph T} and Truhlar, {Donald G.} and Cramer, {Christopher J.} and Lercher, {Johannes A.}",
year = "2019",
month = "6",
day = "12",
doi = "10.1021/jacs.9b02902",
language = "English",
volume = "141",
pages = "9292--9304",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "23",

}

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 -