Charge-Transfer Reductive in Situ Doping of Mesoporous TiO2 Photoelectrodes: Impact of Electrolyte Composition and Film Morphology
Some material properties not only depend on synthesis and processing parameters but also may significantly change during operation. This is particularly true for high-surface-area materials. We used a combined electrochemical and spectroscopic approach to follow the changes in the photoelectrocatalytic activity and in the electronic semiconductor properties of mesoporous TiO2 films upon charge-transfer reductive doping. Shallow donors (i.e., electron/proton pairs) were introduced into the semiconductor by the application of an external potential or, alternatively, by band gap excitation under open circuit conditions. In the latter case, the effective open circuit doping potential depends critically on the electrolyte composition (e.g., the presence of electron or hole acceptors). Transient charge accumulation (electrons and protons) in nanoparticle electrodes results in a photocurrent enhancement that is attributed to the deactivation of recombination centers. In nanotube electrodes, the formation of a space–charge layer results in an additional decrease of charge recombination at positive potentials. Doping is transient in nanoparticle films but turns out to be stable for nanotube arrays.
This article is cited by 11 publications.
- Juan Miguel Jiménez, Daniel Perdolt, Thomas Berger. Reactivity of Hydrogen-Related Electron Centers in Powders, Layers, and Electrodes Consisting of Anatase TiO2 Nanocrystal Aggregates. The Journal of Physical Chemistry C 2021, 125 (25) , 13809-13818. https://doi.org/10.1021/acs.jpcc.1c01580
- Elisabetta Benazzi, Karin Rettenmaier, Thomas Berger, Stefano Caramori, Serena Berardi, Roberto Argazzi, Maurizio Prato, Zois Syrgiannis. Photoelectrochemical Properties of SnO2 Photoanodes Sensitized by Cationic Perylene-Di-Imide Aggregates for Aqueous HBr Splitting. The Journal of Physical Chemistry C 2020, 124 (2) , 1317-1329. https://doi.org/10.1021/acs.jpcc.9b11039
- Coleen T. Nemes, John R. Swierk, Charles A. Schmuttenmaer. A Terahertz-Transparent Electrochemical Cell for In Situ Terahertz Spectroelectrochemistry. Analytical Chemistry 2018, 90 (7) , 4389-4396. https://doi.org/10.1021/acs.analchem.7b04204
- Petr Dzik, Michal Veselý, Oliver Diwald. Fabrication of Metal Oxide Nanostructures by Materials Printing. 2021,,, 229-270. https://doi.org/10.1002/9781119436782.ch7
- Thomas Berger, Oliver Diwald. Characterization of Surfaces and Interfaces. 2021,,, 557-591. https://doi.org/10.1002/9781119436782.ch15
- Maxime E. Dufond, Jean-Noël Chazalviel, Lionel Santinacci. Electrochemical Stability of n-Si Photoanodes Protected by TiO 2 Thin Layers Grown by Atomic Layer Deposition. Journal of The Electrochemical Society 2021, 168 (3) , 031509. https://doi.org/10.1149/1945-7111/abeaf3
- Robert Brüninghoff, Ainoa Paradelo Rodríguez, Ronald P.H. Jong, Jacobus M. Sturm, Uwe Breuer, Caroline Lievens, Adriaan W. Jeremiasse, Guido Mul, Bastian Mei. Electrochemical preparation of defect-engineered titania: Bulk doping versus surface contamination. Applied Surface Science 2021, 539 , 148136. https://doi.org/10.1016/j.apsusc.2020.148136
- Baoshun Liu, Xiujian Zhao, Ivan P. Parkin, Kazuya Nakata. Charge carrier transfer in photocatalysis. 2020,,, 103-159. https://doi.org/10.1016/B978-0-08-102890-2.00004-X
- J.A. Diaz-Real, P. Elsaesser, T. Holm, W. Mérida. Electrochemical reduction on nanostructured TiO2 for enhanced photoelectrocatalytic oxidation. Electrochimica Acta 2020, 329 , 135162. https://doi.org/10.1016/j.electacta.2019.135162
- Jesús Idígoras, Lidia Contreras-Bernal, James M. Cave, Nicola E. Courtier, Ángel Barranco, Ana Borras, Juan R. Sánchez-Valencia, Juan A. Anta, Alison B. Walker. The Role of Surface Recombination on the Performance of Perovskite Solar Cells: Effect of Morphology and Crystalline Phase of TiO 2 Contact. Advanced Materials Interfaces 2018, 5 (21) , 1801076. https://doi.org/10.1002/admi.201801076
- Baoshun Liu, Rui Zhang. Effects of spatial topologies and electron Fermi-level gradient on the photocatalytic efficiency of nano-particulate semiconductors. Physical Chemistry Chemical Physics 2017, 19 (15) , 10116-10124. https://doi.org/10.1039/C7CP00574A