The commercial success of polymer electrolyte fuel cells (PEFCs) depends on the development of Pt-based oxygen reduction reaction (ORR) catalysts with greater activity and stability to reduce the amount of expensive noble metal per device. To advance toward this goal, we have tested a novel class of unsupported bimetallic alloy catalysts (aerogels) as the cathode material in PEFCs under two accelerated stress test conditions and compared it to a state-of-the-art carbon-supported benchmark (Pt/C). The investigated Pt 3 Ni aerogel shows little degradation under high potential conditions (> 1.0 V) which can occur during fuel starvation and start-up/shutdown of the cell. If tested under the same conditions, the Pt/C benchmark displays significant losses of electrochemical surface area and ORR activity due to carbon support corrosion as observed in cross section and transmission electron microscopy analysis. When testing the durability upon extended load cycling (0.6-1.0 V), Pt 3 Ni aerogel demonstrates less stability than Pt/C which is related to the severe Ni leaching from the alloy under such conditions. These findings highlight the advantages of using unsupported ORR catalysts in PEFCs and point to the reduction of non-noble metal dissolution as the next development step. Polymer electrolyte fuel cells (PEFCs) currently rely on large amounts of carbon-supported platinum (Pt/C) catalysts (≈0.4 mg Pt /cm 2 electrode ) to reduce the voltage losses due to the sluggish kinetics of the cathodic oxygen reduction reaction (ORR).1 Recent advancements in minimizing the Pt loading and associated costs were achieved by alloying platinum with other metals like Ni, Cu and Co which increases the Pt mass-specific ORR activity.2 On the other hand, these catalysts suffer from significant corrosion of the carbon support and Pt nanoparticles during PEFC operation which compromises their long-term efficiency and reliability.3 To specifically mitigate the issue of support stability, researchers have developed alternative corrosionresistant supports (e.g. conductive metal oxides 4-7 ), extended metal surfaces (e.g. 3 M nanostructured thin film catalysts 8 ) and unsupported materials (e.g. Pt-coated Ni, Co or Cu nanowires 9-11 ). Pursuing this last strategy, unsupported bimetallic Pt-Ni electrocatalysts with high specific surface area (≈30 m 2 /g Pt ) and nanochain network structure, referred to as aerogels, were synthesized in a previous work.
12These materials reach the U.S. Department of Energy target (DOE; i.e. 440 A/g Pt at 0.9 V vs. the reversible hydrogen electrode (V RHE )) for automotive PEFC application when tested as thin films by the rotating disk electrode (RDE) technique, 13 which is the standard tool employed by the majority of researchers in this field for initial assessment of catalyst activities. Considering that performance figures derived from such RDE experiments, often do not translate fully to the technical system, it is fundamental to also assess activity and durability in PEFCs to evaluate the real application p...