Pt-catalyzed oxidation of PEMFC carbon supports: A path to highly accessible carbon morphologies and implications for start-up/shut-down degradation

The morphology of carbon supports for Pt-based proton-exchange membrane fuel cell (PEMFC) catalysts strongly determines their performance at both low and high current density. Porous carbon supports with internally deposited Pt nanoparticles sustain high kinetic activity by shielding Pt from ionomer adsorption, albeit at the expense of poor oxygen mass transport. This work systematically explores an oxidative pre-treatment of commercial Pt/Ketjenblack, termed localized oxidation, which drastically improves oxygen transport and high current density performance (up to 50% at 0.6 V). The method leverages Pt-catalyzed carbon oxidation in the immediate vicinity of internal Pt particles to increase pore accessibility. We analyze the catalyst morphology via N₂ physisorption and thermogravimetric analysis (TGA), and correlate these results with extensive electrochemical characterization of low-loaded cathodes (0.06 mg_Pt cm^-2). High current density gains are shown to result predominantly from removing microporous constrictions in the primary carbon particle. We further identify a trade-off between Pt particle sintering and pore widening dependent on the oxidation temperature, which defines an optimum degree of oxidation. Finally, we investigate the susceptibility of locally oxidized catalysts towards start-up/shut-down (SUSD) degradation. Although we find modestly accelerated degradation rates at high oxidation temperatures, this does not outweigh the performance benefit imparted by the pre-treatment.