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This content will become publicly available on December 26, 2018

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

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. Also, 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. Here, 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.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [2] ;  [2] ;  [2] ; ORCiD logo [2] ;  [2] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [4]
  1. Northwestern Univ., Evanston, IL (United States). Department of Chemistry
  2. Northwestern Univ., Evanston, IL (United States). Department of Chemistry
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences & Engineering Division
  4. Northwestern Univ., Evanston, IL (United States). Department of Chemistry and Department of Chemical and Biological Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences & Engineering Division; King Abdulaziz Univ., Jeddah (Saudi Arabia). Department of Chemistry, Faculty of Science
Publication Date:
Grant/Contract Number:
AC02-06CH11357; SC0012702; FG02-99ER14999
Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Northwestern University - International Institute for Nanotechnology (IIN); Energy Frontier Research Center, Inorganometallic Catalyst Design Center (ICDC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkene oxidation; catechol; copper catalyst; metal−organic frameworks; mixed-linker; non-innocent; redox-active; UiO-68
OSTI Identifier:
1421963