Alkaline-Metal Cations Affect Pt Deactivation for the Electrooxidation of Small Organic Molecules by Affecting the Formation of Inactive Pt Oxide

The activity of Pt for the electro-oxidation of several organic molecules changes with the cation of the electrolyte. It has been proposed that the underlying reason behind that effect is the so-called noncovalent interactions between the hydrated cations and adsorbed OH (OH_ad). However, there is a lack of spectroscopic evidence for this phenomenon, resulting in an incomplete understanding at the microscopic level of these electrochemical processes. Herein, we explore the electro-oxidation of glycerol (EOG) on platinum (Pt) in LiOH, NaOH and KOH using <i>in situ</i> surface-enhanced infrared absorption spectroscopy in the attenuated total reflectance mode (ATR-SEIRAS) and <i>in situ</i> X-ray absorption spectroscopy (XAS). Our results show that the electrolyte cation influences the rate and potential at which adsorbed CO (CO_ad), a catalytic poison, is formed and oxidized. We attribute this to the cation-dependent stability of oxygenated species on the metallic Pt surface and the different intensities of the electric field at the electrode/electrolyte interface. We also demonstrate that the formation of an inactive Pt oxide layer is indirectly also cation-dependent: the formation of this layer is triggered by the cation-dependent oxidative removal of reaction intermediates (for instance, CO). This phenomenon explains the well-known cation-induced differences in the voltammetric profiles, of not just glycerol, but generally of alcohols and polyols.