Effect of Redox "non-Innocent" Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal-Organic Frameworks

Xuan Zhang, Nicolaas A. Vermeulen, Zhiyuan Huang, Yuexing Cui, Jian Liu, Matthew D. Krzyaniak, Zhanyong Li, Hyunho Noh, Michael R Wasielewski, Massimiliano Delferro, Omar K. Farha

Research output: Contribution to journalArticle

25 Citations (Scopus)

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. 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. 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.

Original languageEnglish
Pages (from-to)635-641
Number of pages7
JournalACS Applied Materials and Interfaces
Volume10
Issue number1
DOIs
Publication statusPublished - Jan 10 2018

Keywords

  • alkene oxidation
  • catechol
  • copper catalyst
  • metal-organic frameworks
  • mixed-linker
  • non-innocent
  • redox-active
  • UiO-68

ASJC Scopus subject areas

  • Materials Science(all)

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  • Cite this

    Zhang, X., Vermeulen, N. A., Huang, Z., Cui, Y., Liu, J., Krzyaniak, M. D., Li, Z., Noh, H., Wasielewski, M. R., Delferro, M., & Farha, O. K. (2018). Effect of Redox "non-Innocent" Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal-Organic Frameworks. ACS Applied Materials and Interfaces, 10(1), 635-641. https://doi.org/10.1021/acsami.7b15326