Installing Heterobimetallic Cobalt-Aluminum Single Sites on a Metal Organic Framework Support

Anthony B. Thompson, Dale R. Pahls, Varinia Bernales, Leighanne C. Gallington, Camille D. Malonzo, Thomas Webber, Stephen J. Tereniak, Timothy C. Wang, Sai Puneet Desai, Zhanyong Li, In Soo Kim, Laura Gagliardi, R. Lee Penn, Karena W. Chapman, Andreas Stein, Omar K. Farha, Joseph T. Hupp, Alex B F Martinson, Connie C. Lu

Research output: Contribution to journalArticlepeer-review

43 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)6753-6762
Number of pages10
JournalChemistry of Materials
Issue number18
StatePublished - Sep 27 2016

Bibliographical note

Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). Parts of this work were performed at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357, and at the University of Minnesota Characterization Facility, which receives partial support from the NSF through the MRSEC, ERC, MRI, and NNIN programs. A. A. Yakovenko assisted with the synchrotron diffraction measurements and DED analysis. Xray crystallographic data have been deposited in the Cambridge Crystallographic Data Centre (CCDC) database (1482959-1482962).

Publisher Copyright:
© 2016 American Chemical Society.


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