Electrochemical Preparation of TiOx-Electrodes: Effect of the Counter Electrode on the Charge Transfer Properties

Sub-stoichiometric titanium dioxide (TiO x ) is known for its corrosion resistance and electrical conductivity. 1 Thus, it is recognized as promising material for (photo-)electrochemical applications and used as protective layer in PEC water splitting or electrode material for water treatment. 1,2 In general, its properties strongly depend on the synthesis and the conductivity of TiO x can be tuned by its Ti/O ratio. 1,3 TiO x is commonly prepared by hydrogenation; 3 however, the requirements for high pressure, high temperature and hydrogen atmosphere are cumbersome imposing a potential safety risk. Over the past years, electrochemical preparation of TiO x via cathodic polarization of TiO 2 substrates became an interesting alternative. 4 Pt is widely used in electrochemistry as counter electrode 5 and frequently applied for TiO x preparation; 4 however, the suitability of Pt as (anodic) counter electrode (CE) is questionable since the stability of Pt is often overestimated. 5 As Pt contamination can severely influence the electrocatalytic properties this study focuses on the preparation of TiO x using three different CE (Pt, Iridium mixed metal oxide, Boron doped diamond) and the influence of the CE will be discussed in detail. It will be shown using state of the art techniques such as SEM, XPS and highly surface sensitive low energy ion scattering (LEIS) spectroscopy that indeed Pt contamination dominates the properties of TiO x (Figure 1a). In contrast, for Iridium mixed metal oxide and Boron doped diamond CEs no related contaminations were observed allowing to determine the intrinsic properties of TiO x electrodes. Using Fe 2 +/3+ redox couple experiments and electrochemical impedance spectroscopy we determined the charge transfer properties of the TiO x electrodes prepared with BDD and IrMMO (Figure 1b). Although both BDD and IrMMO appear to be suited for the preparation of TiO x differences in the doping are observed that will be discussed in detail in this contribution. References: F. C. Walsh and R. G. A. Wills, Electrochim. Acta , 55 , 6342–6351 (2010), doi: 10.1039/c6ra14507h B. Xu, H. Y. Sohn, Y. Mohassab, and Y. Lan, RSC Adv. , 6 , 79706–79722 (2016), doi: 10.1039/c6ra14507h. X. Yan, L. Tian, X. Tan, M Zhou, L. Liu and X. Chen, MRS Commun. , 6 , 192–203 (2016), doi: 10.1557/mrc.2016.33. J. Swaminathan, R. Subbiah, and V. Singaram, ACS Catal. , 6 , 2222–2229 (2016), doi: 10.1021/acscatal.5b02614. J. G. Chen, C. W. Jones, S. Linic, and V. R. Stamenkovic, ACS Catal. , 7 , 6392–6393 (2017), doi: 10.1021/acscatal.7b02839. Figure 1