OH Radical Formation at Distinct Faces of Rutile TiO2 Crystal in the Procedure of Photoelectrochemical Water Oxidation

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Department of Materials Science and Technology, Nagaoka University of Technology, Nagaoka, 940-2188 Japan
*E-mail: [email protected]. Tel./Fax: +81-258-47-9315.
Cite this: J. Phys. Chem. C 2013, 117, 45, 23832–23839
Publication Date (Web):October 10, 2013
Copyright © 2013 American Chemical Society
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It has been believed that the photogenerated OH radicals are major active species which cause photocatalytic oxidation of water. To investigate the actual contribution of OH radicals to the photocatalytic O2 generation, the amount of the OH radicals was measured for the three kinds of rutile TiO2 electrodes having (100), (110), and (001) crystalline surfaces. The current efficiencies for O2 generation measured with an oxygen sensor were almost 100% for all electrodes. However, the current efficiencies for OH radical formation estimated by means of a coumarin fluorescence probe method were less than 1%. Thus, it was experimentally elucidated that the contribution of OH radicals to the O2 production is negligibly small. The amount of OH radical production decreased in the order of (100) > (110) > (001), along with the increase in the efficiency of the O2 production. A plausible mechanism of OH radical formation as a byproduct in the O2 generation process was proposed.

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Experimental data for AFM observation (Figure S1) of three electrodes, the calibration chart for calculating the umbelliferone concentration in 0.1 mM coumarin solution with fluorescence spectra (Figure S2), and the current–voltage curves of theTiO2 rutile (100) and (110) electrodes under UV irradiation and dark condition (Figure S3). This material is available free of charge via the Internet at http://pubs.acs.org.

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