Real-time investigation of reactive oxygen species and radicals evolved from operating Fe–N–C electrocatalysts during the ORR: potential dependence, impact on degradation, and structural comparisons

Abstract

Improving the stability of platinum-group-metal-free (PGM-free) catalysts is a critical roadblock to the development of economically feasible energy storage and conversion technologies. Fe–N–C catalysts, the most promising class of PGM-free catalysts, suffer from rapid degradation. The generation of reactive oxygen species (ROS) during the oxygen reduction reaction (ORR) has been proposed as a central cause of this loss of activity. However, there is insufficient understanding of the generation and dynamics of ROS under catalytic conditions due to the difficulty of detecting and quantifying short-lived ROS such as the hydroxyl radical, OH˙. To accomplish this, we use operando scanning electrochemical microscopy (SECM) to probe the production of radicals by a commercial pyrolyzed Fe–N–C catalyst in real-time using a redox-active spin trap methodology. SECM showed the monotonic production of OH˙ which followed the ORR activity. Our results were thoroughly backed using electron spin resonance confirmation to show that the hydroxyl radical is the dominant radical species produced. Furthermore, OH˙ and H₂O₂ production followed distinct trends. ROS studied as a function of catalyst degradation also showed a decreased production, suggesting its relation to the catalytic activity of the sample. The structural origins of ROS production were also probed using model systems such as iron phthalocyanine (FePc) and Fe₃O₄ nanoparticles, both of which showed significant generation of OH˙ during the ORR. These results provide a comprehensive insight into the critical, yet under-studied, aspects of the production and effects of ROS on electrocatalytic systems and open the door for further mechanistic and kinetic investigation using SECM.