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Title: Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support

Here, a heterobimetallic cobalt-aluminum complex was immobilized onto the metal organic framework NU-1000 using a simple solution-based deposition procedure. Characterization data are consistent with a maximum loading of a single Co-Al complex per Zr 6 node of NU-1000. Furthermore, the data support that the Co-Al bimetallic complex is evenly distributed throughout the NU-1000 particle, binds covalently to the Zr6 nodes, and occupies the NU-1000 apertures with the shortest internode distances (~8.5 Å). Heating the anchored Co-Al complex on NU-1000 at 300 °C for 1 h in air completely removes the organic ligand of the complex without affecting the structural integrity of the MOF support. We propose that a Co-Al oxide cluster is formed in place of the anchored complex in NU-1000 during heating. Collectively, the results suggest that well-defined heterobimetallic complexes can be effective precursors for installing two different metals simultaneously onto a MOF support. The CoAl-functionalized NU-1000 samples catalyze the oxidation of benzyl alcohol to benzaldehyde with tert-butyl hydroperoxide as a stoichiometric oxidant. Density functional theory calculations were performed to elucidate the detailed structures of the Co-Al active sites on the Zr 6-nodes, and a Co-mediated catalytic mechanism is proposed.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [3] ;  [1] ;  [3] ;  [2] ;  [1] ;  [1] ;  [2] ;  [1] ;  [3] ;  [3] ;  [2] ;  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 18; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1356824