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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 31, Number 1
BKCSDE 31(1)
January 20, 2010 

Heterogeneous Electron Transfer at Polyoxometalate-modified Electrode Surfaces
Suhee Choi, Bora Seo, Jongwon Kim*
Electron transfer, Polyoxometalate, Glassy carbon, Au, HOPG
The heterogeneous electron transfer at SiMo12O404? monolayers on GC, HOPG, and Au electrode surfaces are investigated using cyclic voltammetric and electrochemical impedance spectroscopic (EIS) methods. The electron transfer of negatively charged Fe(CN)63? species is retarded at SiMo12O404? -modified electrode surfaces, while that of positively charged Ru(NH3)63+species is accelerated at the modified surfaces. This is due to the electrostatic interactions between SiMo12O404? layers on surfaces and charged redox species. The electron transfer kinetics of a neutral redox species, 1,1’- ferrocenedimethanol (FDM), is not affected by the modification of electrode surfaces with SiMo12O404?, indicating the SiMo12O404? monolayers do not impart barriers to electron transfer of neutral redox species. This is different from the case of thiolate SAMs which always add barriers to electron transfer. The effect of SiMo12O404? layers on the electron transfer of charged redox species is dependent on the kind of electrodes, where HOPG surfaces exhibit marked effects. Possible mechanisms responsible for different electron transfer behaviors at SiMo12O404? layers are proposed.
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