Pivotal Role of Geometry Regulation on O−O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts

Abstract In this study, we highlight the impact of catalyst geometry on the formation of O−O bonds in Cu 2 and Fe 2 catalysts. A series of Cu 2 complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, the catalytic performance of these Cu 2 complexes is enhanced as their molecular skeletons become more rigid, which contrasts with the behavior observed in our previous investigation with Fe 2 analogs. Moreover, mechanistic studies reveal that the reactivity of the bridging O atom results in distinct pathways for O−O bond formation in Cu 2 and Fe 2 catalysts. In Cu 2 systems, the coupling takes place between a terminal Cu III −OH and a bridging μ −O⋅ radical. Whereas in Fe 2 systems, it involves the coupling of two terminal Fe–oxo entities. Furthermore, an in‐depth structure–activity analysis uncovers the spatial geometric prerequisites for the coupling of the terminal OH with the bridging μ −O⋅ radical, ultimately leading to the O−O bond formation. Overall, this study emphasizes the critical role of precisely adjusting the spatial geometry of catalysts to align with the O−O bonding pathway.