Abstract
Nanostructured valve metal oxides have been extensively investigated due to the variety of applications related to their valuable chemical and physical properties, including mechanical and thermal resistance, catalytic and photocatalytic activity, and biocompatibility. The technology to form well defined porous anodic oxides on titanium will strongly benefit from an optimization of the process parameters based on deterministic modelling. The relatively large number of adjustable parameters often precludes the unambiguous interpretation of steady-state and transient electrochemical data in terms of a unique kinetic model.An approach to overcome this ambiguity by parameterization of the models of barrier film growth [1, 2] on Ti and its alloys (Figure 1) using a combination of in-situ EIS in a large frequency range, dynamic high-frequency impedance and photocurrent measurements, combined with ex-situ characterization of the oxides by X-ray photoelectron spectroscopy (XPS) is presented. Additional estimates of kinetic parameters are derived from density functional theory (DFT) modelling of adsorption of water and fluoride on Ti and TiO2 [3, 4]. Ways to extract information on the rate-limiting steps of the process of passive film formation, growth and restructuring are described and the significance of the obtained parameters for the kinetics of barrier film growth and dissolution is outlined. Stancheva, M. Bojinov, Electrochim. Acta 78, 65 (2012).Bojinov, I. Betova, V. Karastoyanov, Electrochim. Acta 344, 136137 (2020).Stancheva, B. Diawara, F. Lebreau, M. Bojinov, J. Electrochem. Soc. 161, E3188 (2014).Betova, M. Bojinov, V. Karastoyanov, M. Stancheva, Computational Mater. Sci.171, 109260 (2020). Acknowledgments: The financial support of the National Science Fund of Bulgaria under contract ДН19/3-2017 „Modeling, optimization and modification of nanoporous anodic oxide films as catalysts for water photoelectrolysis“is gratefully acknowledged. Figure 1
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