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 language | English |
|---|---|
| Pages (from-to) | 6753-6762 |
| Number of pages | 10 |
| Journal | Chemistry of Materials |
| Volume | 28 |
| Issue number | 18 |
| DOIs | |
| Publication status | Published - Sep 27 2016 |
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ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
- Materials Chemistry
Cite this
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 journal › Article
}
TY - JOUR
T1 - Installing Heterobimetallic Cobalt-Aluminum Single Sites on a Metal Organic Framework Support
AU - Thompson, Anthony B.
AU - Pahls, Dale R.
AU - Bernales, Varinia
AU - Gallington, Leighanne C.
AU - Malonzo, Camille D.
AU - Webber, Thomas
AU - Tereniak, Stephen J.
AU - Wang, Timothy C.
AU - Desai, Sai Puneet
AU - Li, Zhanyong
AU - Kim, In Soo
AU - Gagliardi, Laura
AU - Penn, R. Lee
AU - Chapman, Karena W.
AU - Stein, Andreas
AU - Farha, Omar K.
AU - Hupp, Joseph T
AU - Martinson, Alex B F
AU - Lu, Connie C.
PY - 2016/9/27
Y1 - 2016/9/27
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84989184191&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84989184191&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.6b03244
DO - 10.1021/acs.chemmater.6b03244
M3 - Article
AN - SCOPUS:84989184191
VL - 28
SP - 6753
EP - 6762
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 18
ER -