Atomistic Insights into the Degradation of Metal Phthalocyanine Catalysts during Oxygen Reduction Reaction

Oxygen reduction catalysts frequently suffer from degradation under harsh operating conditions, and a limited understanding of the underlying mechanisms hampers the development of effective mitigation strategies. In this study, we integrate first-principles calculations with a time-dependent microkinetic model to investigate the deactivation pathways of six highly active metal phthalocyanines (MPc, M = Cr, Mn, Fe, Ru, Rh, and Ir) during the oxygen reduction reaction (ORR). We quantitatively assess the ORR processes, hydrogen peroxide generation, radical generation, and three primary degradation mechanisms, namely, carbon oxidation, nitrogen protonation, and demetallation, through a reaction network involving 40 chemical species and 75 elementary reactions. Our findings reveal that the dominant degradation mechanism varies significantly across the MPcs. Under typical alkaline conditions, the primary byproducts arise from carbon oxidation, driven by • OH radical attack and structural reorganization of surface adsorbates, and from protonation at either the metal center or nitrogen sites. In the kinetics-controlled region, the ORR activity follows the order of RhPc > IrPc > FePc > MnPc > RuPc > CrPc. Notably, RhPc and IrPc demonstrate both higher ORR activity and greater stability than the widely studied FePc under elevated potentials.