Electrochemical preparation of defect-engineered titania: Bulk doping versus surface contamination

Robert Brüninghoff, Ainoa Paradelo Rodríguez, Ronald P.H. Jong, Jacobus M. Sturm, Uwe Breuer, Caroline Lievens, Adriaan W. Jeremiasse, Guido Mul, Bastian Mei*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Defect-engineered or substoichiometric TiOx is of interest for use in photo- and electrocatalytic processes both as active material and catalyst support. Electrochemical doping of TiO2 via cathodic polarization is an appealing preparation method and frequently employed. Here, we explored the electrochemical preparation of TiOx in an undivided cell using iridium-based (iridium mixed-metal-oxide) and boron doped diamond (BDD) counter electrodes. Cyclic voltammetry and impedance spectroscopy revealed superior charge transfer properties of crystalline TiOx electrodes prepared with BDD (TiOx-BDD). It is shown that the electrochemical properties correlate well with intensities of the H-signals determined using Time of Flight - Secondary Ion Mass Spectrometry (ToF-SIMS). Thus, it is concluded that electrochemical preparation using BDD causes favourable H+ intercalation and/or H diffusion into the sub-surface layers of TiOx. Our extensive analysis using a combination of electrochemical and surface characterization (LEIS and XPS) techniques, additionally suggests that cathodic deposition of Ir, originating from the Ir-based counter electrode, present in sub-ppm concentrations only results in less-efficient doping. Instead in the presence of sub-ppm level Ir contamination hydrogen evolution is favoured during cathodic polarization. The results presented within this study highlight the necessity to use inherently stable counter electrodes for electrochemical preparation and reveal the pronounced influence of trace contamination in electrochemistry in general and the doping mechanism of TiOx electrodes in particular.

Original languageEnglish
Article number148136
JournalApplied surface science
Volume539
Early online date26 Oct 2020
DOIs
Publication statusE-pub ahead of print/First online - 26 Oct 2020

Keywords

  • UT-Hybrid-D
  • Defect-engineered TiO
  • Electrochemical preparation
  • Surface characterization
  • Surface contamination
  • Charge transfer properties

Fingerprint Dive into the research topics of 'Electrochemical preparation of defect-engineered titania: Bulk doping versus surface contamination'. Together they form a unique fingerprint.

Cite this