• Degradation due air/air operation due to startup and shutdown in fuel cell studied. • The effect of platinum loading, and carbon support material is studied. • A segmented cathode hardware is utilized to study the effect along the flow field. • In-situ and ex-situ characterization were correlated to elucidate the degradation. • Limiting the anode's ability to reduce oxygen to water is key to mitigating loss. A B S T R A C T Polymer electrolyte membrane fuel cells have durability limitations associated with the startup and shutdown of the fuel cell, which is critical for real-world vehicle commercialization. During startup or shutdown, there exists an active region (hydrogen/air) and a passive region (air/air) between the cell inlet and outlet. Internal currents are generated in the passive region causing high-potential excursion in the cathode leading to accelerated carbon corrosion. In this study, a segmented cathode hardware is used to evaluate the effect of platinum loading on both cathode and anode, and carbon support material on degradation due to repeated series of startups or shutdowns. In situ losses in the performance and electrochemical surface area were measured spatially, and ex situ analysis of the catalyst layer thickness and platinum particle size was performed to understand the effect of startup or shutdown on different membrane electrode assembly materials. Startup degrades the region near anode outlet more, while shutdown degrades the region near anode inlet more compared to the rest of the electrode. While various system mitigation strategies have been reported in the literature to limit this degradation, one materials mitigation strategy is to limit the anode's ability to reduce oxygen to water through increasing the ratio of platinum loading in the cathode to the anode, or by using a bi-functional catalyst.