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

View Author Information
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
Copyright © 2013 American Chemical Society
Article Views
Read OnlinePDF (927 KB)
Supporting Info (1)»


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.

Supporting Information

Jump To

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

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 17 publications.

  1. María Isabel Díez-García and Roberto Gómez . Investigating Water Splitting with CaFe2O4 Photocathodes by Electrochemical Impedance Spectroscopy. ACS Applied Materials & Interfaces 2016, 8 (33) , 21387-21397.
  2. Mukes Kapilashrami, Yanfeng Zhang, Yi-Sheng Liu, Anders Hagfeldt, and Jinghua Guo . Probing the Optical Property and Electronic Structure of TiO2 Nanomaterials for Renewable Energy Applications. Chemical Reviews 2014, 114 (19) , 9662-9707.
  3. Dejan Cibrev, Milena Jankulovska, Teresa Lana-Villarreal, and Roberto Gómez . Potentiostatic Reversible Photoelectrochromism: An Effect Appearing in Nanoporous TiO2/Ni(OH)2 Thin Films. ACS Applied Materials & Interfaces 2014, 6 (13) , 10304-10312.
  4. Basamat S. Shaheen, Hanadi G. Salem, Mostafa A. El-Sayed, and Nageh K. Allam . Thermal/Electrochemical Growth and Characterization of One-Dimensional ZnO/TiO2 Hybrid Nanoelectrodes for Solar Fuel Production. The Journal of Physical Chemistry C 2013, 117 (36) , 18502-18509.
  5. Guozheng Zhao, Fang Yuan, Huili Li, Jinjian Liu. Photochromism and thermochromism: new strategies for (HV)[Co(H2O)6](p-BDC)2(DMF)·H2O. Journal of Materials Science 2021, 56 (11) , 6912-6921.
  6. Damián Monllor-Satoca, Pedro Bonete, Ridha Djellabi, Giuseppina Cerrato, Lorenza Operti, Roberto Gómez, Claudia Letizia Bianchi. Comparative Photo-Electrochemical and Photocatalytic Studies with Nanosized TiO2 Photocatalysts towards Organic Pollutants Oxidation. Catalysts 2021, 11 (3) , 349.
  7. María Isabel Díez-García, Verónica Celorrio, Laura Calvillo, Devendra Tiwari, Roberto Gómez, David J. Fermín. YFeO3 Photocathodes for Hydrogen Evolution. Electrochimica Acta 2017, 246 , 365-371.
  8. Anthoni B Aritonang, Hedi Surahman, Yuni K Krisnandi, Jarnuzi Gunlazuardi. Photo-electro-catalytic performance of highly ordered nitrogen doped TiO 2 nanotubes array photoanode. IOP Conference Series: Materials Science and Engineering 2017, 172 , 012005.
  9. Xiaoyun Zhang, Dong Li, Jiafeng Wan, Xiujuan Yu. Hydrothermal synthesis of TiO2 nanosheets photoelectrocatalyst on Ti mesh for degradation of norfloxacin: Influence of pickling agents. Materials Science in Semiconductor Processing 2016, 43 , 47-54.
  10. Xianghua Li, Jianqiang Wang, Yihe Zhang, Minhua Cao. Efficient visible-light photocatalytic performance of cuprous oxide porous nanosheet arrays. Materials Research Bulletin 2015, 70 , 728-734.
  11. Majid Mollavali, Cavus Falamaki, Sohrab Rohani. Preparation of multiple-doped TiO2 nanotube arrays with nitrogen, carbon and nickel with enhanced visible light photoelectrochemical activity via single-step anodization. International Journal of Hydrogen Energy 2015, 40 (36) , 12239-12252.
  12. Jianqing Chen, Donghui Yang, Dan Song, Jinghua Jiang, Aibin Ma, Michael Z. Hu, Chaoying Ni. Recent progress in enhancing solar-to-hydrogen efficiency. Journal of Power Sources 2015, 280 , 649-666.
  13. M.I. Díez-García, V. Manzi-Orezzoli, M. Jankulovska, S. Anandan, P. Bonete, R. Gómez, T. Lana-Villarreal. Effects of Ultrasound Irradiation on the Synthesis of Metal Oxide Nanostructures. Physics Procedia 2015, 63 , 85-90.
  14. Dang Duc Vuong, Khuc Quang Trung, Nguyen Hoang Hung, Nguyen Van Hieu, Nguyen Duc Chien. Facile preparation of large-scale α-Fe2O3 nanorod/SnO2 nanorod composites and their LPG-sensing properties. Journal of Alloys and Compounds 2014, 599 , 195-201.
  15. Próspero Acevedo-Peña, Federico González, Gonzalo González, Ignacio González. The effect of anatase crystal orientation on the photoelectrochemical performance of anodic TiO 2 nanotubes. Phys. Chem. Chem. Phys. 2014, 16 (47) , 26213-26220.
  16. Qinghua Chen, Huiling Liu, Yanjun Xin, Xiuwen Cheng. TiO2 nanobelts – Effect of calcination temperature on optical, photoelectrochemical and photocatalytic properties. Electrochimica Acta 2013, 111 , 284-291.
  17. Simonetta Palmas, Michele Mascia, Annalisa Vacca, Ilenia Tredici. Photoelectrocatalytic Performances of Nanostructured/Decorated TiO 2 Electrodes: Effect of Wavelength and Cell Configuration. International Journal of Photoenergy 2013, 2013 , 1-10.