Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework

Takaaki Ikuno, Jian Zheng, Aleksei Vjunov, Maricruz Sanchez-Sanchez, Manuel A. Ortuño, Dale R. Pahls, John L. Fulton, Donald M. Camaioni, Zhanyong Li, Debmalya Ray, B. Layla Mehdi, Nigel D. Browning, Omar K. Farha, Joseph T Hupp, Christopher J. Cramer, Laura Gagliardi, Johannes A. Lercher

Research output: Contribution to journalArticle

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Abstract

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu+ and ∼85% Cu2+. The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu2+ to Cu+. The products, methanol, dimethyl ether, and CO2, were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

Original languageEnglish
Pages (from-to)10294-10301
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number30
DOIs
Publication statusPublished - Aug 2 2017

Fingerprint

Methane
Methanol
Metals
Oxidation
X-Ray Absorption Spectroscopy
Chemical reactivity
Catalysts
X ray absorption spectroscopy
Copper oxides
Atomic layer deposition
Oxides
Density functional theory
Copper
Ethers
Carbon
Atoms
Water

ASJC Scopus subject areas

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

Cite this

Ikuno, T., Zheng, J., Vjunov, A., Sanchez-Sanchez, M., Ortuño, M. A., Pahls, D. R., ... Lercher, J. A. (2017). Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework. Journal of the American Chemical Society, 139(30), 10294-10301. https://doi.org/10.1021/jacs.7b02936

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework. / Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A.; Pahls, Dale R.; Fulton, John L.; Camaioni, Donald M.; Li, Zhanyong; Ray, Debmalya; Mehdi, B. Layla; Browning, Nigel D.; Farha, Omar K.; Hupp, Joseph T; Cramer, Christopher J.; Gagliardi, Laura; Lercher, Johannes A.

In: Journal of the American Chemical Society, Vol. 139, No. 30, 02.08.2017, p. 10294-10301.

Research output: Contribution to journalArticle

Ikuno, T, Zheng, J, Vjunov, A, Sanchez-Sanchez, M, Ortuño, MA, Pahls, DR, Fulton, JL, Camaioni, DM, Li, Z, Ray, D, Mehdi, BL, Browning, ND, Farha, OK, Hupp, JT, Cramer, CJ, Gagliardi, L & Lercher, JA 2017, 'Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework', Journal of the American Chemical Society, vol. 139, no. 30, pp. 10294-10301. https://doi.org/10.1021/jacs.7b02936
Ikuno, Takaaki ; Zheng, Jian ; Vjunov, Aleksei ; Sanchez-Sanchez, Maricruz ; Ortuño, Manuel A. ; Pahls, Dale R. ; Fulton, John L. ; Camaioni, Donald M. ; Li, Zhanyong ; Ray, Debmalya ; Mehdi, B. Layla ; Browning, Nigel D. ; Farha, Omar K. ; Hupp, Joseph T ; Cramer, Christopher J. ; Gagliardi, Laura ; Lercher, Johannes A. / Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 30. pp. 10294-10301.
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