TY - JOUR
T1 - Bias-switchable permselectivity and redox catalytic activity of a ferrocene-functionalized, thin-film metal-organic framework compound
AU - Hod, Idan
AU - Bury, Wojciech
AU - Gardner, Daniel M.
AU - Deria, Pravas
AU - Roznyatovskiy, Vladimir
AU - Wasielewski, Michael R.
AU - Farha, Omar K.
AU - Hupp, Joseph T.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/2/19
Y1 - 2015/2/19
N2 - 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.
AB - 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.
KW - charge hopping
KW - electrocatalysis
KW - metal-organic framework
KW - permselectivity
KW - redox shuttle
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U2 - 10.1021/acs.jpclett.5b00019
DO - 10.1021/acs.jpclett.5b00019
M3 - Article
C2 - 26262471
AN - SCOPUS:84923366420
VL - 6
SP - 586
EP - 591
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 4
ER -