Journal of Physical Chemistry B, Vol.109, No.12, 5836-5841, 2005
Temperature dependence of oxygen reduction activity at Pt-Fe, Pt-Co, and Pt-Ni alloy electrodes
Oxygen reduction reaction (ORR) activity and H2O2 formation at Pt54Fe46, Pt68CO32, and Pt63Ni37 electrodes in 0.1 M HClO4 solution at 20 to 90 degrees C were investigated by using a channel flow double electrode method. In the temperature range of 20-50 degrees C, the apparent rate constants k(app) for ORR at these electrodes were found to be 2.4-4.0 times larger than that at a pure Pt electrode, whereas their apparent activation energies of 41 kJ mol(-1) at -0.525 V vs E degrees (0.760 V vs RHE at 30 degrees C) were comparable to that at the Pt electrode. H2O2 yield was ca. 1.0% at Pt54Fe46 and ca. 0.16% at Pt68CO32 and Pt63Ni37 between 0. 3 and 1.0 V vs RHE. The k(app) values at the alloy electrodes decreased with elevating temperature above 60 degrees C, and settled to almost the same values at the Pt electrode. The H2O2 production was not detected at the alloy electrodes once. probably due to the thickening of the Pt skin-layer by a heated at the high temperature in the solution. considerable dissolution of nonprecious metal components (Fe, Co, Ni) from the alloys.