Why Do Weak-Binding M-N-C Single-Atom Catalysts Possess Anomalously High Oxygen Reduction Activity? (2402.05405v3)

Abstract: Single-atom catalysts (SACs) with metal-nitrogen-carbon (M-N-C) structures are widely recognized as promising candidates in oxygen reduction reactions (ORR). According to the classical Sabatier principle, optimal 3d metal catalysts, such as Fe/Co-N-C, achieve superior catalytic performance due to the moderate binding strength. However, the substantial ORR activity demonstrated by weakly binding M-N-C catalysts such as NiCu-N-C challenges current understandings, emphasizing the need to explore new underlying mechanisms. In this work, we integrated a pH-field coupled microkinetic model with detailed experimental electron state analyses to verify a novel key step in the ORR reaction pathway of weak-binding SACs-the oxygen adsorption at the metal-N bridge site. This step significantly altered the adsorption scaling relations, electric field responses, and solvation effects, further impacting the key kinetic reaction barrier from HOO* to O* and pH-dependent performance. Synchrotron spectra analysis further provides evidence for the new weak-binding M-N-C model, showing an increase in electron density on the anti-bonding pi orbitals of N atoms in weak-binding M-N-C catalysts and confirming the presence of N-O bonds. These findings redefine the understanding of weak-binding M-N-C catalyst behavior, opening up new perspectives for their application in clean energy.