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Title: Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks

Abstract

Two new UiO-68 type of Zr-MOFs featuring redox non-innocent catechol-based linkers of different redox activities have been synthesized through a de novo mixed-linker strategy. Also, metalation of the MOFs with Cu(II) precursors triggers the reduction of Cu(II) by the phenyl-catechol groups to Cu(I) with the concomitant formation of semiquinone radicals as evidenced by EPR and XPS characterization. The MOF-supported catalysts are selective toward the allylic oxidation of cyclohexene and it is found that the presence of in situ-generated Cu(I) species exhibits enhanced catalytic activity as compared to a similar MOF with Cu(II) metalated naphthalenyl-dihydroxy groups. Here, this work unveils the importance of metal-support redox interactions in the catalytic activity of MOF-supported catalysts which are not easily accessible in traditional metal oxide supports.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [2];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Northwestern Univ., Evanston, IL (United States). Department of Chemistry
  2. Northwestern Univ., Evanston, IL (United States). Department of Chemistry
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences & Engineering Division
  4. Northwestern Univ., Evanston, IL (United States). Department of Chemistry and Department of Chemical and Biological Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences & Engineering Division; King Abdulaziz Univ., Jeddah (Saudi Arabia). Department of Chemistry, Faculty of Science
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Northwestern University - International Institute for Nanotechnology (IIN); Energy Frontier Research Center, Inorganometallic Catalyst Design Center (ICDC)
OSTI Identifier:
1421963
Grant/Contract Number:  
AC02-06CH11357; SC0012702; FG02-99ER14999
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkene oxidation; catechol; copper catalyst; metal−organic frameworks; mixed-linker; non-innocent; redox-active; UiO-68

Citation Formats

Zhang, Xuan, Vermeulen, Nicolaas A., Huang, Zhiyuan, Cui, Yuexing, Liu, Jian, Krzyaniak, Matthew D., Li, Zhanyong, Noh, Hyunho, Wasielewski, Michael R., Delferro, Massimiliano, and Farha, Omar K. Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks. United States: N. p., 2017. Web. doi:10.1021/acsami.7b15326.
Zhang, Xuan, Vermeulen, Nicolaas A., Huang, Zhiyuan, Cui, Yuexing, Liu, Jian, Krzyaniak, Matthew D., Li, Zhanyong, Noh, Hyunho, Wasielewski, Michael R., Delferro, Massimiliano, & Farha, Omar K. Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks. United States. doi:10.1021/acsami.7b15326.
Zhang, Xuan, Vermeulen, Nicolaas A., Huang, Zhiyuan, Cui, Yuexing, Liu, Jian, Krzyaniak, Matthew D., Li, Zhanyong, Noh, Hyunho, Wasielewski, Michael R., Delferro, Massimiliano, and Farha, Omar K. Tue . "Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks". United States. doi:10.1021/acsami.7b15326.
@article{osti_1421963,
title = {Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks},
author = {Zhang, Xuan and Vermeulen, Nicolaas A. and Huang, Zhiyuan and Cui, Yuexing and Liu, Jian and Krzyaniak, Matthew D. and Li, Zhanyong and Noh, Hyunho and Wasielewski, Michael R. and Delferro, Massimiliano and Farha, Omar K.},
abstractNote = {Two new UiO-68 type of Zr-MOFs featuring redox non-innocent catechol-based linkers of different redox activities have been synthesized through a de novo mixed-linker strategy. Also, metalation of the MOFs with Cu(II) precursors triggers the reduction of Cu(II) by the phenyl-catechol groups to Cu(I) with the concomitant formation of semiquinone radicals as evidenced by EPR and XPS characterization. The MOF-supported catalysts are selective toward the allylic oxidation of cyclohexene and it is found that the presence of in situ-generated Cu(I) species exhibits enhanced catalytic activity as compared to a similar MOF with Cu(II) metalated naphthalenyl-dihydroxy groups. Here, this work unveils the importance of metal-support redox interactions in the catalytic activity of MOF-supported catalysts which are not easily accessible in traditional metal oxide supports.},
doi = {10.1021/acsami.7b15326},
journal = {ACS Applied Materials and Interfaces},
number = 1,
volume = 10,
place = {United States},
year = {Tue Dec 26 00:00:00 EST 2017},
month = {Tue Dec 26 00:00:00 EST 2017}
}

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