skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. https://www.osti.gov/servlets/purl/1421963.
@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},
issn = {1944-8244},
number = 1,
volume = 10,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Redox‐Reversible 2D Metal–Organic Framework Nanosheets (MONs) Based on the Hydroquinone/Quinone Couple
journal, February 2019

  • Maka, Vijay Kumar; Mukhopadhyay, Arindam; Jindal, Swati
  • Chemistry – A European Journal, Vol. 25, Issue 15
  • DOI: 10.1002/chem.201805188

Redox-active metal–organic frameworks for energy conversion and storage
journal, January 2019

  • Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
  • Journal of Materials Chemistry A, Vol. 7, Issue 28
  • DOI: 10.1039/c9ta04680a

An X-ray Spectral Study of the Electronic Structure of Non-Innocent Mono- and Binuclear Platinum Complexes with N-Phenyl-o-Benzosemiquinonediimine
journal, June 2019

  • Ivanova, T. M.; Sidorov, A. A.; Mazalov, L. N.
  • Journal of Structural Chemistry, Vol. 60, Issue 6
  • DOI: 10.1134/s0022476619060052

Tunable Reduction of 2,4,6-Tri(4-pyridyl)-1,3,5-Triazine: From Radical Anion to Diradical Dianion to Radical Metal-Organic Framework
journal, October 2019

  • Tang, Shuxuan; Ruan, Huapeng; Feng, Rui
  • Angewandte Chemie International Edition, Vol. 58, Issue 50
  • DOI: 10.1002/anie.201910468

UNAM-1: a robust Cu I and Cu II containing 3D-hydrogen-bonded framework with permanent porosity and reversible SO 2 sorption
journal, January 2019

  • Domínguez-González, Ricardo; Rojas-León, Irán; Martínez-Ahumada, Eva
  • Journal of Materials Chemistry A, Vol. 7, Issue 47
  • DOI: 10.1039/c9ta07834g

Tunable Reduction of 2,4,6-Tri(4-pyridyl)-1,3,5-Triazine: From Radical Anion to Diradical Dianion to Radical Metal-Organic Framework
journal, October 2019

  • Tang, Shuxuan; Ruan, Huapeng; Feng, Rui
  • Angewandte Chemie International Edition, Vol. 58, Issue 50
  • DOI: 10.1002/anie.201910468

Redox‐Reversible 2D Metal–Organic Framework Nanosheets (MONs) Based on the Hydroquinone/Quinone Couple
journal, February 2019

  • Maka, Vijay Kumar; Mukhopadhyay, Arindam; Jindal, Swati
  • Chemistry – A European Journal, Vol. 25, Issue 15
  • DOI: 10.1002/chem.201805188

Redox-active metal–organic frameworks for energy conversion and storage
journal, January 2019

  • Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
  • Journal of Materials Chemistry A, Vol. 7, Issue 28
  • DOI: 10.1039/c9ta04680a

UNAM-1: a robust Cu I and Cu II containing 3D-hydrogen-bonded framework with permanent porosity and reversible SO 2 sorption
journal, January 2019

  • Domínguez-González, Ricardo; Rojas-León, Irán; Martínez-Ahumada, Eva
  • Journal of Materials Chemistry A, Vol. 7, Issue 47
  • DOI: 10.1039/c9ta07834g

An X-ray Spectral Study of the Electronic Structure of Non-Innocent Mono- and Binuclear Platinum Complexes with N-Phenyl-o-Benzosemiquinonediimine
journal, June 2019

  • Ivanova, T. M.; Sidorov, A. A.; Mazalov, L. N.
  • Journal of Structural Chemistry, Vol. 60, Issue 6
  • DOI: 10.1134/s0022476619060052