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Title: Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports

Abstract

NU-1000, a mesoporous metal–organic framework (MOF) featuring hexazirconium oxide nodes and 3 nm wide channels, was infiltrated with a reactive dicobalt complex to install dicobalt active sites onto the MOF nodes. The anchoring of the dicobalt complex onto NU-1000 occurred with a nearly ideal stoichiometry of one bimetallic complex per node and with the cobalt evenly distributed throughout the MOF particle. To access thermally robust multimetallic sites on an all-inorganic support, the modified NU-1000 materials containing either the dicobalt complex, or an analogous cobalt–aluminum species, were nanocast with silica. The resulting materials feature Co 2or Co–Al bimetallated hexazirconium oxide clusters within a silica matrix. The cobalt-containing materials are competent catalysts for the selective oxidation of benzyl alcohol to benzaldehyde. Catalytic activity depends on the number of cobalt ions per node, but does not vary significantly between the NU-1000 and silica supports. Hence, the multimetallic oxide clusters remain site-isolated and substrate-accessible within the nanocast materials.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [2]; ORCiD logo [2];  [1];  [3]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Department of Chemistry; University of Minnesota; Minneapolis; USA
  2. Department of Chemistry; Northwestern University; Evanston; USA
  3. Department of Chemistry; Northwestern University; Evanston; USA; Department of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1469881
DOE Contract Number:  
SC0012702
Resource Type:
Journal Article
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 201; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), materials and chemistry by design, synthesis (novel materials)

Citation Formats

Desai, Sai Puneet, Malonzo, Camille D., Webber, Thomas, Duan, Jiaxin, Thompson, Anthony B., Tereniak, Stephen J., DeStefano, Matthew R., Buru, Cassandra T., Li, Zhanyong, Penn, R. Lee, Farha, Omar K., Hupp, Joseph T., Stein, Andreas, and Lu, Connie C.. Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports. United States: N. p., 2017. Web. doi:10.1039/c7fd00055c.
Desai, Sai Puneet, Malonzo, Camille D., Webber, Thomas, Duan, Jiaxin, Thompson, Anthony B., Tereniak, Stephen J., DeStefano, Matthew R., Buru, Cassandra T., Li, Zhanyong, Penn, R. Lee, Farha, Omar K., Hupp, Joseph T., Stein, Andreas, & Lu, Connie C.. Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports. United States. https://doi.org/10.1039/c7fd00055c
Desai, Sai Puneet, Malonzo, Camille D., Webber, Thomas, Duan, Jiaxin, Thompson, Anthony B., Tereniak, Stephen J., DeStefano, Matthew R., Buru, Cassandra T., Li, Zhanyong, Penn, R. Lee, Farha, Omar K., Hupp, Joseph T., Stein, Andreas, and Lu, Connie C.. Sun . "Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports". United States. https://doi.org/10.1039/c7fd00055c.
@article{osti_1469881,
title = {Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports},
author = {Desai, Sai Puneet and Malonzo, Camille D. and Webber, Thomas and Duan, Jiaxin and Thompson, Anthony B. and Tereniak, Stephen J. and DeStefano, Matthew R. and Buru, Cassandra T. and Li, Zhanyong and Penn, R. Lee and Farha, Omar K. and Hupp, Joseph T. and Stein, Andreas and Lu, Connie C.},
abstractNote = {NU-1000, a mesoporous metal–organic framework (MOF) featuring hexazirconium oxide nodes and 3 nm wide channels, was infiltrated with a reactive dicobalt complex to install dicobalt active sites onto the MOF nodes. The anchoring of the dicobalt complex onto NU-1000 occurred with a nearly ideal stoichiometry of one bimetallic complex per node and with the cobalt evenly distributed throughout the MOF particle. To access thermally robust multimetallic sites on an all-inorganic support, the modified NU-1000 materials containing either the dicobalt complex, or an analogous cobalt–aluminum species, were nanocast with silica. The resulting materials feature Co2or Co–Al bimetallated hexazirconium oxide clusters within a silica matrix. The cobalt-containing materials are competent catalysts for the selective oxidation of benzyl alcohol to benzaldehyde. Catalytic activity depends on the number of cobalt ions per node, but does not vary significantly between the NU-1000 and silica supports. Hence, the multimetallic oxide clusters remain site-isolated and substrate-accessible within the nanocast materials.},
doi = {10.1039/c7fd00055c},
url = {https://www.osti.gov/biblio/1469881}, journal = {Faraday Discussions},
issn = {1359-6640},
number = ,
volume = 201,
place = {United States},
year = {2017},
month = {1}
}

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