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.

doi:10.1021/acs.chemmater.6b03244

Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support

Journal Article · Mon Aug 22 00:00:00 EDT 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b03244· OSTI ID:1356824

Thompson, Anthony B. ^[1]; Pahls, Dale R. ^[1]; Bernales, Varinia ^[1]; Gallington, Leighanne C. ^[2]; Malonzo, Camille D. ^[1]; Webber, Thomas ^[1]; Tereniak, Stephen J. ^[1]; Wang, Timothy C. ^[3]; Desai, Sai Puneet ^[1]; Li, Zhanyong ^[3]; Kim, In Soo ^[2]; Gagliardi, Laura ^[1]; Penn, R. Lee ^[1]; Chapman, Karena W. ^[2]; Stein, Andreas ^[1]; Farha, Omar K. ^[3]; Hupp, Joseph T. ^[3]; Martinson, Alex B. F. ^[2]; Lu, Connie C. ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Northwestern Univ., Evanston, IL (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; SC0012702

OSTI ID:: 1356824

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 18 Vol. 28; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1482959: Experimental Crystal Structure Determination: EXERAC : (N'-(pyridin-2-yl)-N-(2-((pyridin-2-yl)amino)ethyl)-N-(2-(pyridin-2-ylamino)ethyl)ethane-1,2-diaminato)-aluminium Thompson, Anthony; Pahls, Dale; Bernales, Varinia https://doi.org/10.5517/ccdc.csd.cc1ls4dx The current record is supplemented by this dataset	dataset	May 2016
CCDC 1482960: Experimental Crystal Structure Determination: EXEREG : (μ-N'-(pyridin-2-yl)-N,N-bis(2-(pyridin-2-ylamino)ethyl)ethane-1,2-diamine)-chloro-aluminium-cobalt Space Group: P 21/n (14), Cell: a 14.511(2)Å b 9.9585(14)Å c 15.004(2)Å, α 90.00° β 101.548(2)° γ 90.00° Thompson, Anthony B.; Pahls, Dale R.; Bernales, Varinia https://doi.org/10.5517/ccdc.csd.cc1ls4fy The current record is supplemented by this dataset	dataset	May 2016
CCDC 1482961: Experimental Crystal Structure Determination: EXERIK : (μ-N'-(pyridin-2-yl)-N,N-bis(2-(pyridin-2-ylamino)ethyl)ethane-1,2-diamine)-methyl-aluminium-cobalt benzene solvate Thompson, Anthony; Pahls, Dale; Bernales, Varinia https://doi.org/10.5517/ccdc.csd.cc1ls4gz The current record is supplemented by this dataset	dataset	May 2016
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Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support

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