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Title: Metal–organic framework supported cobalt catalysts for the oxidative dehydrogenation of propane at low temperature

Here, 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 themore » observed catalytic activity at low temperature.« less
Authors:
ORCiD logo [1] ;  [1] ;  [2] ;  [3] ;  [4] ;  [1] ; ORCiD logo [5] ;  [5] ;  [5] ; ORCiD logo [6] ;  [6] ;  [1] ;  [7]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Supercomputing Inst. and Chemical Theory Center
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Supercomputing Inst. and Chemical Theory Center
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  6. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Supercomputing Inst. and Chemical Theory Center
  7. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
Publication Date:
OSTI Identifier:
1333972
Grant/Contract Number:
SC0012702; AC02-06CH11357
Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Research Org:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY