Journal of Catalysis, Vol.310, 37-44, 2014
Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface Mn-II catalyst covalently attached to TiO2 nanoparticles
A manganese complex covalently attached to a TiO2 electrode via a light-absorbing organic linker (L) was used in the photooxidation of 2',7'-dihydrodichlorofluorescein (H2DCF). Significant and sustained photocurrent was observed upon visible-light illumination of the fully assembled anode in the presence of the substrate. The two-electron, two-proton oxidation of H2DCF yields the fluorescent compound, 2',7'-dichlorofluorescein (DCF). Our studies suggest that the MnII-L-TiO2 architecture is an effective photoanode for multielectron chemistry, as production of DCF under visible-light illumination exceeds yields observed for bare TiO2 as well as Zn-II-L-TiO2 anodes. The turn-on fluorescent behavior of H2DCF upon oxidation makes it an excellent substrate for the study of new photoanodes. The high fluorescence quantum yield of DCF allows for nanomolar sensitivity and real-time monitoring of substrate oxidation. (C) 2013 Elsevier Inc. All rights reserved.