Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 6, Issue 4, Pages 586-591Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b00019
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-FG02-87ER13808, DE-FG02-99ER14999]
- Northwestern University
- U.S-Israel Fulbright program
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The installation of ferrocene molecules within the wide-channel metal-organic framework (MOP) compound, NU-1000, and subsequent configuration of the modified MOF as thin-film coatings on electrodes renders the MOF electroactive in the vicinity of the ferrocenium/ferrocene (Fc(+)/Fc) redox potential due to redox hopping between anchored Fc(+/0) species. The observation of effective site-to-site redox hopping points to the potential usefulness of the installed species as a redox shuttle in photoelectrochemical or electrocatalytic systems. At low supporting electrolyte concentration, we observe bias-tunable ionic permselectivity; films are blocking toward solution cations when the MOF is in the ferrocenium form but permeable when in the ferrocene form. Additionally, with ferrocene-functionalized films, we observe that the MOF's pyrene-based linkers, which are otherwise reversibly electroactive, are now redox-silent. Linker electroactivity is fully recovered, however, when the electrolyte concentration is increased 10 fold, that is, to a concentration similar to or exceeding that of an anchored shuttle molecule. The findings have clear implications for the design and use of MOF-based sensors, electrocatalysts, and photoelectrochemical devices.
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