Generation Pathway of Hydroxyl Radical in Fe/N/C-Based Oxygen Reduction Electrocatalysts under Acidic Media.

The identification of the generation pathway of •OH radical during the oxygen reduction reaction (ORR) is critical because it determines which strategy should be adopted to minimize these corrosive species. In this way, researchers can develop a more stable Fe/N/C ORR catalyst or a catalyst layer in the proton exchange membrane fuel cells (PEMFCs). To date, this critical problem has still been unresolved. Herein, the generation of the •OH radical during the acidic ORR was mimicked by using two known pathways, that is, the Fenton (and Fenton-like) and the electrochemical reduction of H2O2(H2O2-ECR) process. The latter was determined as the main generation pathway of •OH radical below 30 °C. As the temperature surpassed 30 °C, the H2O2-ECR process began to lose its dominance because of the appearance of a third so-far unknown generation pathway. This work lays a basis for future development of radical elimination strategies to stabilize a Fe/N/C ORR catalyst or a catalyst layer in PEMFCs.