Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature

Zhanyong Li, Aaron W. Peters, Varinia Bernales, Manuel A. Ortuño, Neil M. Schweitzer, Matthew R. Destefano, Leighanne C. Gallington, Ana E. Platero-Prats, Karena W. Chapman, Christopher J. Cramer, Laura Gagliardi, Joseph T Hupp, Omar K. Farha

Research output: Contribution to journalArticle

86 Citations (Scopus)

Abstract

Zr-based metal-organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.

Original languageEnglish
Pages (from-to)31-38
Number of pages8
JournalACS Central Science
Volume3
Issue number1
DOIs
Publication statusPublished - Jan 25 2017

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Propane
Dehydrogenation
Cobalt
Metals
Catalysts
Propylene
Catalyst activity
Chemical activation
Temperature
X ray absorption spectroscopy
Atomic layer deposition
Catalyst selectivity
Energy barriers
Catalyst supports
Catalysis
Activation energy
Ions
Crystalline materials
propylene

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Li, Z., Peters, A. W., Bernales, V., Ortuño, M. A., Schweitzer, N. M., Destefano, M. R., ... Farha, O. K. (2017). Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature. ACS Central Science, 3(1), 31-38. https://doi.org/10.1021/acscentsci.6b00290

Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature. / Li, Zhanyong; Peters, Aaron W.; Bernales, Varinia; Ortuño, Manuel A.; Schweitzer, Neil M.; Destefano, Matthew R.; Gallington, Leighanne C.; Platero-Prats, Ana E.; Chapman, Karena W.; Cramer, Christopher J.; Gagliardi, Laura; Hupp, Joseph T; Farha, Omar K.

In: ACS Central Science, Vol. 3, No. 1, 25.01.2017, p. 31-38.

Research output: Contribution to journalArticle

Li, Z, Peters, AW, Bernales, V, Ortuño, MA, Schweitzer, NM, Destefano, MR, Gallington, LC, Platero-Prats, AE, Chapman, KW, Cramer, CJ, Gagliardi, L, Hupp, JT & Farha, OK 2017, 'Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature', ACS Central Science, vol. 3, no. 1, pp. 31-38. https://doi.org/10.1021/acscentsci.6b00290
Li, Zhanyong ; Peters, Aaron W. ; Bernales, Varinia ; Ortuño, Manuel A. ; Schweitzer, Neil M. ; Destefano, Matthew R. ; Gallington, Leighanne C. ; Platero-Prats, Ana E. ; Chapman, Karena W. ; Cramer, Christopher J. ; Gagliardi, Laura ; Hupp, Joseph T ; Farha, Omar K. / Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature. In: ACS Central Science. 2017 ; Vol. 3, No. 1. pp. 31-38.
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AU - Schweitzer, Neil M.

AU - Destefano, Matthew R.

AU - Gallington, Leighanne C.

AU - Platero-Prats, Ana E.

AU - Chapman, Karena W.

AU - Cramer, Christopher J.

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AB - Zr-based metal-organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.

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