Bias-switchable permselectivity and redox catalytic activity of a ferrocene-functionalized, thin-film metal-organic framework compound

Idan Hod, Wojciech Bury, Daniel M. Gardner, Pravas Deria, Vladimir Roznyatovskiy, Michael R. Wasielewski, Omar K. Farha, Joseph T. Hupp

Research output: Contribution to journalArticle

80 Citations (Scopus)

Abstract

The installation of ferrocene molecules within the wide-channel metal-organic framework (MOF) 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.

Original languageEnglish
Pages (from-to)586-591
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume6
Issue number4
DOIs
Publication statusPublished - Feb 19 2015

Keywords

  • charge hopping
  • electrocatalysis
  • metal-organic framework
  • permselectivity
  • redox shuttle

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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