(354g) Durable and Highly Active PGM-Free Cathode Catalysts in Competition with Platinum for Pemfcs

Atomically dispersed and nitrogen-coordinated single iron sites (FeN4) embedded in carbon (Fe-N-C) catalysts are the most promising platinum group metal (PGM)-free catalysts. However, they have yet to match their Pt counterparts for oxygen reduction reaction (ORR) activity and stability in proton exchange membrane fuel cells (PEMFCs). Here, we developed viable Fe-N-C catalysts, which, for the first time, demonstrated competitive activity to that of Pt/C catalysts and dramatically enhanced stability and durability under practical PEMFC operating conditions. The most active Fe-N-C catalyst achieved a record half-wave potential (E1/2 = 0.915 V vs. RHE at 0.6 mgcatcm-2) and an ORR mass activity of 10.5 mA mgcat at 0.9 V in (RDE) tests, exceeding a Pt/C baseline catalyst (60 µgPt cm-2) by 40 mV in acidic electrolytes. This compelling activity of the Fe-N-C catalyst in aqueous acids on rotating disk electrode (RDE) was successfully transferred to fuel cell membrane electrode assembly (MEAs), generating an initial current density of 44.2 mA cm-2 exceeding the U.S. DOE 2025 target (i.e., 44 mA cm-2) at 0.9 VIR-free under O2. Under practical hydrogen-air conditions, record 151 mA cm-2 at 0.8 V and peak power density of 601 mW cm-2 were achieved. Importantly, we discovered that depositing nitrogen-carbon species on the catalyst surface via chemical vapor deposition (CVD) dramatically enhanced catalyst stability, evidenced by performance durability after accelerated stress tests (30 000 square-wave voltage cycles under H2/air) and long-term steady-state life tests (> 300 hours at 0.67 V). Innovative identical location-scanning transmission electron microscopy (IL-STEM) experiments confirmed that the CVD process leads to deposition of nitrogen-doped carbon onto the catalyst surfaces. Along with theoretical modeling, a reconstruction of the carbon structure adjacent to FeN4 sites leads to increased robustness against demetallation and carbon oxidation. This work opens new avenues for developing earth-abundant iron-based catalysts with extraordinary activity and stability, thus competing with Pt and addressing the cost barrier of current PEMFCs.