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

10 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

Fingerprint

Catalyst supports
Copper
Catalyst activity
Metals
Oxides
Paramagnetic resonance
X ray photoelectron spectroscopy
Oxidation
Oxidation-Reduction
catechol

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

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 journalArticle

Zhang, X, Vermeulen, NA, Huang, Z, Cui, Y, Liu, J, Krzyaniak, MD, Li, Z, Noh, H, Wasielewski, MR, Delferro, M & Farha, OK 2018, 'Effect of Redox "non-Innocent" Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal-Organic Frameworks', ACS Applied Materials and Interfaces, vol. 10, no. 1, pp. 635-641. https://doi.org/10.1021/acsami.7b15326
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.
@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 = "alkene oxidation, catechol, copper catalyst, metal-organic frameworks, mixed-linker, non-innocent, redox-active, UiO-68",
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.}",
year = "2018",
month = "1",
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",

}

TY - JOUR

T1 - Effect of Redox "non-Innocent" Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal-Organic Frameworks

AU - Zhang, Xuan

AU - Vermeulen, Nicolaas A.

AU - Huang, Zhiyuan

AU - Cui, Yuexing

AU - Liu, Jian

AU - Krzyaniak, Matthew D.

AU - Li, Zhanyong

AU - Noh, Hyunho

AU - Wasielewski, Michael R

AU - Delferro, Massimiliano

AU - Farha, Omar K.

PY - 2018/1/10

Y1 - 2018/1/10

N2 - 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.

AB - 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.

KW - alkene oxidation

KW - catechol

KW - copper catalyst

KW - metal-organic frameworks

KW - mixed-linker

KW - non-innocent

KW - redox-active

KW - UiO-68

UR - http://www.scopus.com/inward/record.url?scp=85040310838&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85040310838&partnerID=8YFLogxK

U2 - 10.1021/acsami.7b15326

DO - 10.1021/acsami.7b15326

M3 - Article

VL - 10

SP - 635

EP - 641

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 1

ER -