Charge-Transfer Reductive in Situ Doping of Mesoporous TiO2 Photoelectrodes: Impact of Electrolyte Composition and Film Morphology

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Departamento de Sistemas Físicos, Químicos y Naturales, Área de Química Física, Universidad Pablo de Olavide, Ctra. Utrera, km 1, E-41013 Sevilla, Spain
Department of Chemistry and Physics of Materials, University of Salzburg, Hellbrunnerstraße 34/III, A-5020 Salzburg, Austria
*E-mail: [email protected]. Phone: +43-662-8044-5931.
Cite this: J. Phys. Chem. C 2016, 120, 49, 27882–27894
Publication Date (Web):November 22, 2016
https://doi.org/10.1021/acs.jpcc.6b09926
Copyright © 2016 American Chemical Society
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Abstract

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.

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  • Further electrochemical and spectroelectrochemical data as well as Raman spectra of pristine and electrochemically doped TiO2 films (PDF)

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