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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

Thompson, Anthony B., Pahls, Dale R., Bernales, Varinia, Gallington, Leighanne C., Malonzo, Camille D., Webber, Thomas, Tereniak, Stephen J., Wang, Timothy C., Desai, Sai Puneet, Li, Zhanyong, Kim, In Soo, Gagliardi, Laura, Penn, R. Lee, Chapman, Karena W., Stein, Andreas, Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., and Lu, Connie C.. Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support. United States: N. p., Web. doi:10.1021/acs.chemmater.6b03244.
Thompson, Anthony B., Pahls, Dale R., Bernales, Varinia, Gallington, Leighanne C., Malonzo, Camille D., Webber, Thomas, Tereniak, Stephen J., Wang, Timothy C., Desai, Sai Puneet, Li, Zhanyong, Kim, In Soo, Gagliardi, Laura, Penn, R. Lee, Chapman, Karena W., Stein, Andreas, Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., & Lu, Connie C.. Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support. United States. doi:10.1021/acs.chemmater.6b03244.
Thompson, Anthony B., Pahls, Dale R., Bernales, Varinia, Gallington, Leighanne C., Malonzo, Camille D., Webber, Thomas, Tereniak, Stephen J., Wang, Timothy C., Desai, Sai Puneet, Li, Zhanyong, Kim, In Soo, Gagliardi, Laura, Penn, R. Lee, Chapman, Karena W., Stein, Andreas, Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., and Lu, Connie C.. 2016. "Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support". United States. doi:10.1021/acs.chemmater.6b03244. https://www.osti.gov/servlets/purl/1356824.
@article{osti_1356824,
title = {Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support},
author = {Thompson, Anthony B. and Pahls, Dale R. and Bernales, Varinia and Gallington, Leighanne C. and Malonzo, Camille D. and Webber, Thomas and Tereniak, Stephen J. and Wang, Timothy C. and Desai, Sai Puneet and Li, Zhanyong and Kim, In Soo and Gagliardi, Laura and Penn, R. Lee and Chapman, Karena W. and Stein, Andreas and Farha, Omar K. and Hupp, Joseph T. and Martinson, Alex B. F. and Lu, Connie C.},
abstractNote = {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 Zr6 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 Zr6-nodes, and a Co-mediated catalytic mechanism is proposed.},
doi = {10.1021/acs.chemmater.6b03244},
journal = {Chemistry of Materials},
number = 18,
volume = 28,
place = {United States},
year = {2016},
month = {8}
}