Carbon nitride supported Fe₂ cluster catalysts with superior performance for alkene epoxidation

Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a "precursor-preselected" wet-chemistry strategy to synthesize highly dispersed Fe₂ clusters that are supported on mesoporous carbon nitride (mpg-C₃N₄). The obtained Fe₂/mpg-C₃N₄ sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe₂ clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd₂ and Ir₂, which lays the foundation for discovering diatomic cluster catalysts.