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

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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10.1021/acsami.7b15326

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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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