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

doi:10.1021/acsami.7b15326

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

Northwestern University

Research output: Contribution to journal › Article

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 language	English
Pages (from-to)	635-641
Number of pages	7
Journal	ACS Applied Materials and Interfaces
Volume	10
Issue number	1
DOIs	https://doi.org/10.1021/acsami.7b15326
Publication status	Published - Jan 10 2018

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Keywords

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

ASJC Scopus subject areas

Materials Science(all)

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

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

In: ACS Applied Materials and Interfaces, Vol. 10, No. 1, 10.01.2018, p. 635-641.

Research output: Contribution to journal › Article

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. In: ACS Applied Materials and Interfaces. 2018 ; Vol. 10, No. 1. pp. 635-641.

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10.1021/acsami.7b15326