Northwestern Univ., Evanston, IL (United States). Department of Chemistry
Northwestern Univ., Evanston, IL (United States). Department of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences & Engineering Division
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
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.
Zhang, Xuan, et al. "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, Dec. 2017. 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. (2017). Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks. ACS Applied Materials and Interfaces, 10(1). https://doi.org/10.1021/acsami.7b15326
Zhang, Xuan, Vermeulen, Nicolaas A., Huang, Zhiyuan, et al., "Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks," ACS Applied Materials and Interfaces 10, no. 1 (2017), https://doi.org/10.1021/acsami.7b15326
@article{osti_1421963,
author = {Zhang, Xuan and Vermeulen, Nicolaas A. and Huang, Zhiyuan and Cui, Yuexing and Liu, Jian and Krzyaniak, Matthew D. and Li, Zhanyong and Noh, Hyunho and Wasielewski, Michael R. and Delferro, Massimiliano and others},
title = {Effect of Redox “Non-Innocent” Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal–Organic Frameworks},
annote = {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.},
doi = {10.1021/acsami.7b15326},
url = {https://www.osti.gov/biblio/1421963},
journal = {ACS Applied Materials and Interfaces},
issn = {ISSN 1944-8244},
number = {1},
volume = {10},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2017},
month = {12}}
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Inorganometallic Catalyst Design Center (ICDC)
Sponsoring Organization:
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)
Grant/Contract Number:
AC02-06CH11357; SC0012702; FG02-99ER14999
OSTI ID:
1421963
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 1 Vol. 10; ISSN 1944-8244