Charge heterogenized PtFe clusters defy activity–selectivity trade-offs in propane dehydrogenation

Propane dehydrogenation is a pivotal industrial reaction, yet its efficiency is fundamentally constrained by the persistent scaling relation between propane activation and propylene desorption. Here, we transcend this compromise by deliberately constructing charge-state heterogeneity of silica-supported subnanometric PtFe clusters. Through synergistic Pt–Fe alloying and Pt–O–Fe interfacial bonding, we concurrently stabilize electron-rich (Ptδ−) and electron-deficient (Ptδ+) sites within a single catalytic ensemble. This architectural design enables the catalyst to achieve ~99% propylene selectivity at near-thermodynamic equilibrium conversion (~60% at 600 °C) with an ultralow Pt loading of 0.1 wt%, demonstrating high catalytic performance under reaction conditions. Mechanistic studies reveal that Ptδ− sites promote C–H bond cleavage via an electron-withdrawing effect that depletes σ-bond electron density, while neighboring Ptδ+ sites facilitate propylene desorption by modulating d–π orbital interactions. This work establishes charge-state heterogeneity as a versatile principle for circumventing scaling relations in catalytic alkane transformations. Propane dehydrogenation is a pivotal industrial reaction, yet its efficiency is fundamentally constrained by the persistent scaling relation between propane activation and propylene desorption. Here, the authors construct charge-state heterogeneity in silica supported subnanometric PtFe clusters.