ORR activity and stability of carbon supported Pt3Y thin films in PEMFCs

In order to investigate stability of oxygen reduction reaction (ORR) on a Pt3Y thin film under relevant fuel cell conditions, we performed an accelerated stress test (AST) consisting of 3600 potential cycles between 0.4 and 1.4 V at 1 V s-1 in a single proton exchange membrane fuel cell (PEMFC). The ORR activities were evaluated via polarization curves before and after the AST. Electrochemical active surface area (ECSA) was obtained by CO -stripping voltammetry whereas the morphological changes were monitored by means of scanning electron mi-croscopy (SEM) and transmission electron microscopy (TEM). Variations in surface composition and electronic structures were evaluated by energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). After AST, the polarization curves show loss of ORR activity in all voltages for both Pt and Pt3Y. Except at very high voltages (E > 0.85 V-RHE), the ORR activity of Pt3Y after AST is very close to that of Pt before AST. This correlates well with the results from the deconvolution of Pt-4f XPS spectra where the binding energy of metallic Pt in Pt3Y is comparable to pure Pt (71.22 eV). SEM and TEM images demonstrate that the morphologies of the aged Pt3Y and as-sputtered Pt are similar, whereas EDX results confirm a steady bulk composition of Pt3Y thin films throughout the entire electrochemical test. By correlating all these results, we conclude that the loss of ORR activity for Pt3Y is due to an increase in the thickness of the Pt overlayer which induces a relaxation of the Pt overlayer decreasing the compressive strain effect. For pure Pt, the loss of ORR activity is associated with a growth of the Pt domains associated with Ostwald ripening process.