@article{b1d9ddcbdaf942afb426e62191b1b7ce,
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. 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.",
keywords = "UiO-68, alkene oxidation, catechol, copper catalyst, metal-organic frameworks, mixed-linker, non-innocent, redox-active",
author = "Xuan Zhang and Vermeulen, {Nicolaas A.} and Zhiyuan Huang and Yuexing Cui and Jian Liu and Krzyaniak, {Matthew D.} and Zhanyong Li and Hyunho Noh and Wasielewski, {Michael R.} and Massimiliano Delferro and Farha, {Omar K.}",
note = "Funding Information: The synthesis and catalysis work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DESC0012702 (O.K.F. and M.D.). The EPR work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE under grant no. DE-FG02-99ER14999 (M.R.W.). Argonne National Laboratory is supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. This work made use of the IMSERC, J. B. Cohen X-ray Diffraction, EPIC, and KECK II facilities of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.",
year = "2018",
month = jan,
day = "10",
doi = "10.1021/acsami.7b15326",
language = "English",
volume = "10",
pages = "635--641",
journal = "ACS applied materials & interfaces",
issn = "1944-8244",
publisher = "American Chemical Society",
number = "1",
}