Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (E-p, 1.10 <= E-p <= 1.50 V), polarization time (t(p), 100 <= t(p) <= 104 s), and temperature (T, 278 <= T <= 333 K). The critical thicknesses (X-1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (d(ox)). Because X-1 > d(ox) for the entire range of E-p, t(p), and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Pt delta+-O delta- surface dipole (mu(PtO)), and the potential drop (V-ox) and electric field (E-ox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide. (C) 2014 AIP Publishing LLC.