Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN4)-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm–2 at 0.7 V under HDV conditions (0.25 mgPt cm–2 and 250 kPaabs pressure) and retaining 1.20 A cm–2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. The first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.