Selective Catalytic Behavior Induced by Crystal-Phase Transformation in Well-Defined Bimetallic Pt-Sn Nanocrystals

The Pt-Sn bimetallic system is a much studied and commercially used catalyst for propane dehydrogenation. The traditionally prepared catalyst, however, suffers from inhomogeneity and phase separation of the active Pt-Sn phase. Colloidal chemistry offers a route for the synthesis of Pt-Sn bimetallic nanoparticles (NPs) in a systematic, well-defined, tailored fashion over conventional methods. Here, the successful synthesis of well-defined ≈2 nm Pt, PtSn, and Pt₃ Sn nanocrystals with distinct crystallographic phases is reported; hexagonal close packing (hcp) PtSn and fcc Pt₃ Sn show different activity and stability depending on the hydrogen-rich or poor environment in the feed. Moreover, face centred cubic (fcc) Pt₃ Sn/Al₂ O₃ , which exhibited the highest stability compared to hcp PtSn, shows a unique phase transformation from an fcc phase to an L1₂ -ordered superlattice. Contrary to PtSn, H₂ cofeeding has no effect on the Pt₃ Sn deactivation rate. The results reveal structural dependency of the probe reaction, propane dehydrogenation, and provide a fundamental understanding of the structure-performance relationship on emerging bimetallic systems.