Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique

Platinum electrocatalysts supported on high surface area and Vulcan carbon blacks (Pt/HSC, Pt/V) were characterized in rotating disk electrode (RDE) setups for electrochemical area (ECA) and oxygen reduction reaction (ORR) area specific activity (SA) and mass specific activity (MA) at 0.9 V. Films fabricated using several ink formulations and film-drying techniques were characterized for a statistically significant number of independent samples. The highest quality Pt/HSC films exhibited MA 870 ± 91 mA/mgPt and SA 864 ± 56 μA/cm² Pt while Pt/V had MA 706 ± 42 mA/mgPt and SA 1120 ± 70 μA/cm² Pt when measured in 0.1 M HClO₄, 20 mV/s, 100 kPa O₂and 23±2°C. An enhancement factor of 2.8 in themeasured SA was observable on eliminating Nafion ionomer and employing extremely thin, uniform films (~4.5 μg/cm² Pt) of Pt/HSC. The ECA for Pt/HSC (99 ± 7 m2/gPt) and Pt/V (65 ± 5 m²/gPt) were statistically invariant and insensitive to film uniformity/thickness/fabrication technique; accordingly, enhancements in MA are wholly attributable to increases in SA. Impedance measurements coupled with scanning electron microscopy were used to de-convolute the losses within the catalyst layer and ascribed to the catalyst layer resistance, oxygen diffusion, and sulfonate anion adsorption/blocking. The ramifications of these results for proton exchange membrane fuel cells have also been examined.