The Oxidation of Platinum under Wet Conditions Observed by Electrochemical X-ray Photoelectron Spectroscopy

During the electrochemical reduction of oxygen, platinum catalysts are often (partially) oxidized. While these platinum oxides are thought to play a crucial role in fuel cell degradation, their nature remains unclear. Here, we studied the electrochemical oxidation of Pt nanoparticles using in situ XPS. When the particles were sandwiched between a graphene sheet and a proton exchange membrane that is wetted from the back, a confined electrolyte layer was formed, allowing us to probe the electrocatalyst under wet conditions. We show that the surface oxide formed at the onset of Pt oxidation has a mixed Ptδ+/Pt²⁺/Pt⁴⁺ composition. The formation of this surface oxide is suppressed when a Br-containing membrane is chosen due to adsorption of Br on Pt. Time-resolved measurements show that oxidation is fast for nanoparticles: even bulk PtO₂· nH₂O growth occurs on the subminute time scale. The fast formation of Pt⁴⁺ species in both surface and bulk oxide form suggests that Pt⁴⁺-oxides are likely formed (or reduced) even in the transient processes that dominate Pt electrode degradation.