TY - JOUR
T1 - Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts
AU - Lee, Sungsik
AU - Halder, Avik
AU - Ferguson, Glen A.
AU - Seifert, Sönke
AU - Winans, Randall E.
AU - Teschner, Detre
AU - Schlögl, Robert
AU - Papaefthimiou, Vasiliki
AU - Greeley, Jeffrey
AU - Curtiss, Larry A.
AU - Vajda, Stefan
N1 - Funding Information:
The authors thank Drs. Jeffrey W. Elam and Joseph A. Libera for providing the ALD— coated substrates. The work at Argonne was supported by the US Department of Energy, BES Materials Sciences under Contract DEAC02–06CH11357 with UChicago Argonne, LLC, operator of Argonne National Laboratory. The work at the Advance Photon Source (beamline 12-ID-C) was supported by the US Department of Energy, Scientific User Facilities under Contract DEAC02–06CH11357 with UChicago Argonne, LLC, operator of Argonne National Laboratory. A.H. thanks for the support provided by the Air Force Office of Scientific Research. We thank Helmholtz-Zentrum Berlin for allocation of synchrotron radiation beamtime.
Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - 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 °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.
AB - 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 °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.
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U2 - 10.1038/s41467-019-08819-5
DO - 10.1038/s41467-019-08819-5
M3 - Article
C2 - 30814524
AN - SCOPUS:85062284960
VL - 10
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 954
ER -