Influence of pH on Surface States Behavior in TiO2 Nanotubes

View Author Information
CNRS UPR15, Laboratoire Interfaces et Systèmes Electrochimiques, F-75005 Paris, France
UPMC Univ Paris 06, UPR15, LISE, 4 place Jussieu, F-75005 Paris, France
§ Fondazione Bruno Kessler, Via Sommarive, 18, 38123 Povo, Trento, Italy
Cite this: J. Phys. Chem. C 2012, 116, 42, 22139–22148
Publication Date (Web):October 8, 2012
https://doi.org/10.1021/jp3060312
Copyright © 2012 American Chemical Society
Article Views
931
Altmetric
-
Citations
LEARN ABOUT THESE METRICS
Read OnlinePDF (2 MB)

Abstract

The key aspects related to surface states present on an anodically formed TiO2 nanotube array are here discussed. Impedance measurements performed on similar layers, in solutions at different pH, evidenced quite different behaviors and conducting properties. The comparison between the surface state capacitances at three different pH values showed that surface states have to be correlated with hydroxyl groups at the surface of TiO2. They are characterized by a broad distribution in energy in the band gap. Under polarization in alkaline solution, charge transfer then mainly occurs through the surface states. The situation is quite different in acidic solutions in which a low density of surface states was measured and in which proton insertion and negative charge storage in the tubular layer is responsible for the high doping level of the tube walls and band bending in a narrow space charge zone in the walls. In neutral solutions at pH close to the zero-charge pH, only the bottom of the tubes is active, and a localized state attributed to the adsorption of undissociated water molecules is observed.

Cited By


This article is cited by 22 publications.

  1. Kiran Pal Singh, Choel-Hwan Shin, Ha-Young Lee, Fatemeh Razmjooei, Apurba Sinhamahapatra, Joonhee Kang, Jong-Sung Yu. TiO2/ZrO2 Nanoparticle Composites for Electrochemical Hydrogen Evolution. ACS Applied Nano Materials 2020, 3 (4) , 3634-3645. https://doi.org/10.1021/acsanm.0c00346
  2. Heng Zhu, Shicheng Yan, Zhaosheng Li, and Zhigang Zou . Back Electron Transfer at TiO2 Nanotube Photoanodes in the Presence of a H2O2 Hole Scavenger. ACS Applied Materials & Interfaces 2017, 9 (39) , 33887-33895. https://doi.org/10.1021/acsami.7b09827
  3. Jayashree Swaminathan, Ravichandran Subbiah, and Vengatesan Singaram . Defect-Rich Metallic Titania (TiO1.23)—An Efficient Hydrogen Evolution Catalyst for Electrochemical Water Splitting. ACS Catalysis 2016, 6 (4) , 2222-2229. https://doi.org/10.1021/acscatal.5b02614
  4. H. Cachet and E. M. M. Sutter . Kinetics of Water Oxidation at TiO2 Nanotube Arrays at Different pH Domains Investigated by Electrochemical and Light-Modulated Impedance Spectroscopy. The Journal of Physical Chemistry C 2015, 119 (45) , 25548-25558. https://doi.org/10.1021/acs.jpcc.5b06103
  5. Atiđa Selmani, Mario Špadina, Milivoj Plodinec, Ida Delač Marion, Marc Georg Willinger, Johannes Lützenkirchen, Harry D. Gafney, and Engelbert Redel . An Experimental and Theoretical Approach to Understanding the Surface Properties of One-Dimensional TiO2 Nanomaterials. The Journal of Physical Chemistry C 2015, 119 (34) , 19729-19742. https://doi.org/10.1021/acs.jpcc.5b02027
  6. 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. https://doi.org/10.1021/cr5000893
  7. Antonio Abate, Derek J. Hollman, Joël Teuscher, Sandeep Pathak, Roberto Avolio, Gerardino D’Errico, Giuseppe Vitiello, Simona Fantacci, and Henry J. Snaith . Protic Ionic Liquids as p-Dopant for Organic Hole Transporting Materials and Their Application in High Efficiency Hybrid Solar Cells. Journal of the American Chemical Society 2013, 135 (36) , 13538-13548. https://doi.org/10.1021/ja406230f
  8. G.G. Bessegato, M.D. Cooke, P.A. Christensen, D. Wood, M.V.B. Zanoni. Synthesis and electrochemical characterization of Si/TiO2/Au composite anode: Efficient oxygen evolution and hydroxyl radicals generation. Electrochimica Acta 2021, 370 , 137742. https://doi.org/10.1016/j.electacta.2021.137742
  9. Jayashree Swaminathan, Ashokkumar Meiyazhagan. Characterization of Electrocatalyst. 2020,,, 425-451. https://doi.org/10.1007/978-3-030-27161-9_17
  10. Waseem Haider, U. H. Shah, Ishraq Shabib, K. M. Deen. Formation of nanotubes on commercially pure titanium at high potentials (=10 V) and their electrochemical response. Materials Research Express 2019, 6 (6) , 065050. https://doi.org/10.1088/2053-1591/aaf754
  11. Alysson Stefan Martins, Paulo Jorge Marques Cordeiro-Junior, Guilherme Garcia Bessegato, Jussara Fernandes Carneiro, Maria Valnice Boldrin Zanoni, Marcos Roberto de Vasconcelos Lanza. Electrodeposition of WO3 on Ti substrate and the influence of interfacial oxide layer generated in situ: A photoelectrocatalytic degradation of propyl paraben. Applied Surface Science 2019, 464 , 664-672. https://doi.org/10.1016/j.apsusc.2018.09.054
  12. Clément Maheu, Luis Cardenas, Eric Puzenat, Pavel Afanasiev, Christophe Geantet. UPS and UV spectroscopies combined to position the energy levels of TiO 2 anatase and rutile nanopowders. Physical Chemistry Chemical Physics 2018, 20 (40) , 25629-25637. https://doi.org/10.1039/C8CP04614J
  13. Teyyebah Soltani, Ahmad Tayyebi, Byeong-Kyu Lee. Efficient promotion of charge separation with reduced graphene oxide (rGO) in BiVO4/rGO photoanode for greatly enhanced photoelectrochemical water splitting. Solar Energy Materials and Solar Cells 2018, 185 , 325-332. https://doi.org/10.1016/j.solmat.2018.05.050
  14. Sun Hee Yoon, Rand ElShorafa, Mary Katbeh, Dong Suk Han, Hye Won Jeong, Hyunwoong Park, Ahmed Abdel-Wahab. Effect of shape-driven intrinsic surface defects on photocatalytic activities of titanium dioxide in environmental application. Applied Surface Science 2017, 423 , 71-77. https://doi.org/10.1016/j.apsusc.2017.06.147
  15. Juanrong Chen, Fengxian Qiu, Ying Zhang, Jianzheng Liang, Huijun Zhu, Shunsheng Cao. Enhanced supercapacitor performances using C-doped porous TiO 2 electrodes. Applied Surface Science 2015, 356 , 553-560. https://doi.org/10.1016/j.apsusc.2015.08.114
  16. Bo Xu, Erik Gabrielsson, Majid Safdari, Ming Cheng, Yong Hua, Haining Tian, James M. Gardner, Lars Kloo, Licheng Sun. 1,1,2,2-Tetrachloroethane (TeCA) as a Solvent Additive for Organic Hole Transport Materials and Its Application in Highly Efficient Solid-State Dye-Sensitized Solar Cells. Advanced Energy Materials 2015, 5 (10) , 1402340. https://doi.org/10.1002/aenm.201402340
  17. Zhen Li, Youting Ding, Weijun Kang, Cui Li, Dong Lin, Xueyuan Wang, Zhiwen Chen, Minghong Wu, Dengyu Pan. Reduction Mechanism and Capacitive Properties of Highly Electrochemically Reduced TiO2 Nanotube Arrays. Electrochimica Acta 2015, 161 , 40-47. https://doi.org/10.1016/j.electacta.2014.12.132
  18. Qiang Zhu, Changsheng Xie, Huayao Li, Chaoqun Yang, Dawen Zeng. A novel planar integration of all-solid-state capacitor and photodetector by an ultra-thin transparent sulfated TiO 2 film. Nano Energy 2014, 9 , 252-263. https://doi.org/10.1016/j.nanoen.2014.08.002
  19. Rongjun Pan, Yucheng Wu, Zhenglin Li, Zhijie Fang. Effect of irradiation on deposition of CdS in fabricating co-axial heterostructure of TiO2 nanotube arrays via chemical deposition. Applied Surface Science 2014, 292 , 886-891. https://doi.org/10.1016/j.apsusc.2013.12.073
  20. Zhengkai Guo, Xuemin Li, Xuehua Zhang, Zishen Guan, Tao He. Controlled morphology modulation of anodic TiO2 nanotubes via changing the composition of organic electrolytes. Physical Chemistry Chemical Physics 2014, 16 (23) , 11502. https://doi.org/10.1039/c4cp00816b
  21. JianHua Liao, RenShi Luo, Yin Bao Li, Jian Zhang. Preparation of highly photocatalytically active rutile titania nanorods decorated with anatase nanoparticles produced by a titanyl-oxalato complex solution. Materials Science in Semiconductor Processing 2013, 16 (6) , 2032-2038. https://doi.org/10.1016/j.mssp.2013.07.038
  22. Próspero Acevedo-Peña, Ignacio González. TiO 2 Nanotubes Formed in Aqueous Media: Relationship between Morphology, Electrochemical Properties and Photoelectrochemical Performance for Water Oxidation. Journal of The Electrochemical Society 2013, 160 (8) , H452-H458. https://doi.org/10.1149/2.060308jes