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

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

Open Access

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

Author(s) -

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

Publication year - 2017

Publication title -

acs applied materials and interfaces

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 2.535

H-Index - 228

eISSN - 1944-8252

pISSN - 1944-8244

DOI - 10.1021/acsami.7b15326

Subject(s) - redox , catalysis , catechol , metalation , copper , metal organic framework , materials science , metal , linker , allylic rearrangement , cyclohexene , combinatorial chemistry , inorganic chemistry , photochemistry , chemistry , organic chemistry , adsorption , computer science , operating system

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.

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