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 journalArticle

21 Citations (Scopus)

Abstract

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
Pages (from-to)6753-6762
Number of pages10
JournalChemistry of Materials
Volume28
Issue number18
DOIs
Publication statusPublished - Sep 27 2016

Fingerprint

Cobalt
Aluminum
Metals
Benzyl Alcohol
tert-Butylhydroperoxide
Heating
Coal
Structural integrity
Oxidants
Oxides
Density functional theory
Alcohols
Ligands
Oxidation
Air
benzaldehyde

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Thompson, A. B., Pahls, D. R., Bernales, V., Gallington, L. C., Malonzo, C. D., Webber, T., ... Lu, C. C. (2016). Installing Heterobimetallic Cobalt-Aluminum Single Sites on a Metal Organic Framework Support. Chemistry of Materials, 28(18), 6753-6762. https://doi.org/10.1021/acs.chemmater.6b03244

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

In: Chemistry of Materials, Vol. 28, No. 18, 27.09.2016, p. 6753-6762.

Research output: Contribution to journalArticle

Thompson, AB, Pahls, DR, Bernales, V, Gallington, LC, Malonzo, CD, Webber, T, Tereniak, SJ, Wang, TC, Desai, SP, Li, Z, Kim, IS, Gagliardi, L, Penn, RL, Chapman, KW, Stein, A, Farha, OK, Hupp, JT, Martinson, ABF & Lu, CC 2016, 'Installing Heterobimetallic Cobalt-Aluminum Single Sites on a Metal Organic Framework Support', Chemistry of Materials, vol. 28, no. 18, pp. 6753-6762. https://doi.org/10.1021/acs.chemmater.6b03244
Thompson AB, Pahls DR, Bernales V, Gallington LC, Malonzo CD, Webber T et al. Installing Heterobimetallic Cobalt-Aluminum Single Sites on a Metal Organic Framework Support. Chemistry of Materials. 2016 Sep 27;28(18):6753-6762. https://doi.org/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. In: Chemistry of Materials. 2016 ; Vol. 28, No. 18. pp. 6753-6762.
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