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Title: Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts

Abstract

The discovery of more efficient, economical, and selective catalysts for oxidative dehydrogenation is of immense economic importance. However, the temperatures required for this reaction are typically high, often exceeding 400 degrees C. Herein, we report the discovery of subnanometer sized cobalt oxide clusters for oxidative dehydrogenation of cyclohexane that are active at lower temperatures than reported catalysts, while they can also eliminate the combustion channel. These results found for the two cluster sizes suggest other subnanometer size (CoO)x clusters will also be active at low temperatures. The high activity of the cobalt clusters can be understood on the basis of density functional studies that reveal highly active under-coordinated cobalt atoms in the clusters and show that the oxidized nature of the clusters substantially decreases the binding energy of the cyclohexene species which desorb from the cluster at low temperature.

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [2];  [2];  [3];  [4];  [1];  [5]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Fritz-Haber-Institut der Max-Planck Gesellschaft, Berlin (Germany); Max-Planck-Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)
  3. University of Strasbourg (France)
  4. Purdue Univ., West Lafayette, IN (United States)
  5. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR)
OSTI Identifier:
1500014
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lee, Sungsik, Halder, Avik, Ferguson, Glen A., Seifert, Sönke, Winans, Randall E., Teschner, Detre, Schlögl, Robert, Papaefthimiou, Vasiliki, Greeley, Jeffrey, Curtiss, Larry A., and Vajda, Stefan. Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts. United States: N. p., 2019. Web. doi:10.1038/s41467-019-08819-5.
Lee, Sungsik, Halder, Avik, Ferguson, Glen A., Seifert, Sönke, Winans, Randall E., Teschner, Detre, Schlögl, Robert, Papaefthimiou, Vasiliki, Greeley, Jeffrey, Curtiss, Larry A., & Vajda, Stefan. Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts. United States. doi:10.1038/s41467-019-08819-5.
Lee, Sungsik, Halder, Avik, Ferguson, Glen A., Seifert, Sönke, Winans, Randall E., Teschner, Detre, Schlögl, Robert, Papaefthimiou, Vasiliki, Greeley, Jeffrey, Curtiss, Larry A., and Vajda, Stefan. Wed . "Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts". United States. doi:10.1038/s41467-019-08819-5. https://www.osti.gov/servlets/purl/1500014.
@article{osti_1500014,
title = {Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts},
author = {Lee, Sungsik and Halder, Avik and Ferguson, Glen A. and Seifert, Sönke and Winans, Randall E. and Teschner, Detre and Schlögl, Robert and Papaefthimiou, Vasiliki and Greeley, Jeffrey and Curtiss, Larry A. and Vajda, Stefan},
abstractNote = {The discovery of more efficient, economical, and selective catalysts for oxidative dehydrogenation is of immense economic importance. However, the temperatures required for this reaction are typically high, often exceeding 400 degrees C. Herein, we report the discovery of subnanometer sized cobalt oxide clusters for oxidative dehydrogenation of cyclohexane that are active at lower temperatures than reported catalysts, while they can also eliminate the combustion channel. These results found for the two cluster sizes suggest other subnanometer size (CoO)x clusters will also be active at low temperatures. The high activity of the cobalt clusters can be understood on the basis of density functional studies that reveal highly active under-coordinated cobalt atoms in the clusters and show that the oxidized nature of the clusters substantially decreases the binding energy of the cyclohexene species which desorb from the cluster at low temperature.},
doi = {10.1038/s41467-019-08819-5},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {2}
}

Journal Article:
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Figures / Tables:

Fig. 1 Fig. 1: Simplified reaction scheme of the ODH of cyclohexane

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.