Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

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Institut Universitari d’Electroquímica i Departament de Química Física, Universitat d’Alacant, Apartat 99, E-03080 Alacant, Spain
Cite this: J. Phys. Chem. C 2013, 117, 8, 4024–4031
Publication Date (Web):January 31, 2013
https://doi.org/10.1021/jp311068m
Copyright © 2013 American Chemical Society
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Abstract

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

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Morphological effect of the ultrasonic bath treatment; dependence of the NT length and the charge of the accumulation region on the anodization time; TEM images of decorated NTs; discussion about the electroactivity of the NWs inside the NTs; CVs for a NT electrode prior and after decoration with anatase NWs in the presence/absence of oxalic acid; CVs for a NT electrode prior and after decoration with rutile NWs. This material is available free of charge via the Internet at http://pubs.acs.org.

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