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Title: Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

Abstract

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Using difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clustersmore » are active for propane ODH after thermal activation under O2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [4]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-ray Science Division
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOD; ational Science Foundation (NSF); Ministry of Economy and Knowledge from the Catalan Government; Ministry of Science and Technology (Taiwan)
OSTI Identifier:
1419945
Grant/Contract Number:  
AC02-06CH11357; SC0012702
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 42; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Zhanyong, Peters, Aaron W., Platero-Prats, Ana E., Liu, Jian, Kung, Chung-Wei, Noh, Hyunho, DeStefano, Matthew R., Schweitzer, Neil M., Chapman, Karena W., Hupp, Joseph T., and Farha, Omar K. Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane. United States: N. p., 2017. Web. https://doi.org/10.1021/jacs.7b09365.
Li, Zhanyong, Peters, Aaron W., Platero-Prats, Ana E., Liu, Jian, Kung, Chung-Wei, Noh, Hyunho, DeStefano, Matthew R., Schweitzer, Neil M., Chapman, Karena W., Hupp, Joseph T., & Farha, Omar K. Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane. United States. https://doi.org/10.1021/jacs.7b09365
Li, Zhanyong, Peters, Aaron W., Platero-Prats, Ana E., Liu, Jian, Kung, Chung-Wei, Noh, Hyunho, DeStefano, Matthew R., Schweitzer, Neil M., Chapman, Karena W., Hupp, Joseph T., and Farha, Omar K. Wed . "Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane". United States. https://doi.org/10.1021/jacs.7b09365. https://www.osti.gov/servlets/purl/1419945.
@article{osti_1419945,
title = {Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane},
author = {Li, Zhanyong and Peters, Aaron W. and Platero-Prats, Ana E. and Liu, Jian and Kung, Chung-Wei and Noh, Hyunho and DeStefano, Matthew R. and Schweitzer, Neil M. and Chapman, Karena W. and Hupp, Joseph T. and Farha, Omar K.},
abstractNote = {Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Using difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)},
doi = {10.1021/jacs.7b09365},
journal = {Journal of the American Chemical Society},
number = 42,
volume = 139,
place = {United States},
year = {2017},
month = {10}
}

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