Performance and characterization of a Pt-Sn(oxidized)/C cathode catalyst with a SnO2-decorated Pt3Sn nanostructure for oxygen reduction reaction in a polymer electrolyte fuel cell.

We have prepared and characterized a SnO2-decorated Pt-Sn(oxidized)/C cathode catalyst in a polymer electrolyte fuel cell (PEFC). Oxygen reduction reaction (ORR) performance of Pt/C (TEC10E50E) remained almost unchanged or even tended to reduce in repeated I-V load cycles, whereas the I-V load performance of the Pt-Sn(oxidized)/C prepared by controlled oxidation of a Pt-Sn alloy/C sample with the Pt3Sn phase revealed a significant increase with increasing I-V load cycles. The unique increase in the ORR performance of the Pt-Sn(oxidized)/C catalyst was ascribed to a promoting effect of SnO2 nano-islands formed on the surface of Pt3Sn core nanoparticles. Also in a rotating disk electrode (RDE) setup, the mass activity of an oxidized Pt3Sn/C catalyst was initially much lower than that of a Pt/C catalyst, but it increased remarkably after 5000 rectangular durability cycles and became higher than that of the fresh Pt/C. The maximum power density per electrochemical surface area for the Pt-Sn(oxidized)/C catalyst in a PEFC was about 5 times higher than that for the Pt/C catalyst at 0.1-0.8 A cm(-2) of the current density. In situ X-ray absorption near-edge structure (XANES) analysis at the Pt LIII-edge in increasing/decreasing potential operations and at the Sn K-edge in the I-V load cycles revealed a remarkable suppression of Pt oxidation compared with the Pt/C catalyst at higher potentials and no change in the Sn oxidation state, respectively, resulting in higher performance and stability of the Pt-Sn(oxidized)/C catalyst due to the SnO2 nano-islands under the PEFC operation conditions. The SnO2 nano-island decorated Pt-Sn(oxidized)/C catalyst with a Pt3Sn alloy nanostructure is regarded as a promising candidate for a PEFC cathode catalyst.