Potentiostatic and Potential Cycling Dissolution of Polycrystalline Platinum and Platinum Nano-Particle Fuel Cell Catalysts

The dissolution of Pt in aqueous electrolytes has been studied for over forty years, most recently in the context of understanding the observed loss in electrochemically-active surface area (ECA) of cathode electrocatalysts in polymer electrolyte fuel cells. Despite extensive research, there are many unresolved issues regarding the dissolution of nano-particle Pt, such as the source of the observed potential dependence of potentiostatic and potential cycling dissolution rates. To help resolve these issues, in this paper we present results of measurements of the concentration of dissolved Pt and Pt dissolution rates for carbon-supported platinum nano - particles (Pt/C) in dilute perchloric acid, as a mimic of the PEFC cathode environment, as a function of potential and upper potential limit of potential cycling. Also presented, for comparison, are results of similar studies on polycrystalline platinum. In situ Pt L III X-ray absorption spectroscopy was used to determine the extent of oxidation, the coordination environment, and loss of Pt from the Pt nano-particles to elucidate the mechanism of Pt dissolution. Based on the correlation of these studies with those presented in the literature, mechanisms for Pt dissolution under potentiostatic and potential cycling conditions are proposed.