Abstract
The development of alternative alloy catalysts with high activity, surpassing platinum group metals, for the oxygen reduction reaction (ORR) is urgently needed in the field of electrocatalysis. The Ag-based single-atom alloy (AgSAA) cluster has been proposed as a promising catalyst for the ORR; however, enhancing its activity under operational conditions remains challenging due to limited insights into its actual active site. Here, we demonstrate that the operando formation of the MO (x) (OH) (y) complex serves as the key active site for catalyzing the ORR over AgSAA cluster catalysts, as revealed through comprehensive neural network potential molecular dynamics simulations combined with first-principles calculations. The volcano plot of the ORR over the MO (x) (OH) (y) complex addresses the gaps inherent in traditional metallic alloy models for pure AgSAA cluster catalysts in ORR catalysis. The appropriate orbital hybridization between OH and the dopant metal in the MO (x) (OH) (y) complexes indicated that the Ag(54)Co(1), Ag(54)Pd(1), and Ag(54)Au(1) clusters are optimal AgSAA catalysts for the ORR. Our work underscores the significance of theoretical modeling considering the reaction atmosphere in uncovering the true active site for the ORR, which can be extended to other reaction systems for rational catalyst design.