Correlating oxygen functionalities and electrochemical durability of carbon supports for electrocatalysts

Achieving high durability of the polymer electrolyte membrane (PEM) fuel cell catalysts remains a major challenge. While most of the research focuses on the active phase, carbon support remains overlooked. In this study durability of carbon support materials for Pt alloy nanoparticles is critically evaluated. First graphene derivative (GD) based carbon supports with different chemical properties are prepared and utilized along with widely used commercial carbon black (CB) material. High-temperature electrochemical accelerated degradation tests (HT-ADTs) combined with X-ray photoelectron spectroscopy (XPS) show that the total amount of oxygen functionalities, the type of oxygen functionalities, and sp2 carbon content play a crucial role in carbon support durability. The observations were confirmed with the direct online measurements of carbon corrosion via an advanced in-situ technique - an electrochemical cell coupled with a mass spectrometer (EC-MS). We report that increasing the content of sp2 carbon and decreasing carboxyl functional groups have the most beneficial effect on stability. The study provides important guidelines for tailoring the carbon support properties and their relationship to the durability of the electrocatalyst, which could be crucial for producing more stable catalysts and achieving the Department of Energy's fuel cell system lifetime targets. Moreover, the innovative carbon design approach presented here could be applied in other fields such as batteries, supercapacitors, sensors and others.