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

doi:10.1021/acs.chemmater.6b03244

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^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

58 Scopus citations

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 (US)
Pages (from-to)	6753-6762
Number of pages	10
Journal	Chemistry of Materials
Volume	28
Issue number	18
DOIs	https://doi.org/10.1021/acs.chemmater.6b03244
State	Published - Sep 27 2016

Funding

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).

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.6b03244

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Thompson, A. B., Pahls, D. R., Bernales, V., Gallington, L. C., Malonzo, C. D., Webber, T., Tereniak, S. J., Wang, T. C., Desai, S. P., Li, Z., Kim, I. S., Gagliardi, L., Penn, R. L., Chapman, K. W., Stein, A., Farha, O. K., Hupp, J. T., Martinson, A. B. F., & 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

@article{8d5a3972352c4831960cf445d553c555,

title = "Installing Heterobimetallic Cobalt-Aluminum Single Sites on a Metal Organic Framework Support",

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 {\AA}). 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.",

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

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = sep,

day = "27",

doi = "10.1021/acs.chemmater.6b03244",

language = "English (US)",

volume = "28",

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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

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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.

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DO - 10.1021/acs.chemmater.6b03244

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JO - Chemistry of Materials

JF - Chemistry of Materials

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ER -

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

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CCDC 1482961: Experimental Crystal Structure Determination

CCDC 1482960: Experimental Crystal Structure Determination

CCDC 1482959: Experimental Crystal Structure Determination

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

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CCDC 1482961: Experimental Crystal Structure Determination

CCDC 1482960: Experimental Crystal Structure Determination

CCDC 1482959: Experimental Crystal Structure Determination

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