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 | |
| 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
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
}
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
AN - SCOPUS:85040310838
VL - 10
SP - 635
EP - 641
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
SN - 1944-8244
IS - 1
ER -