Kinetic diffusion-controlled synthesis of twinned intermetallic nanocrystals for CO-resistant catalysis

Intermetallic catalysts are of immense interest, but how heterometals diffuse and related interface structure remain unclear when there exists a strong metal-support interaction. Here, we developed a kinetic diffusion-controlled method and synthesized intermetallic Pt₂Mo nanocrystals with twin boundaries on mesoporous carbon (Pt₂Mo/C). The formation of small-sized twinned intermetallic nanocrystals is associated with the strong Mo-C interaction-induced slow Mo diffusion and the heterogeneity of alloying, which is revealed by an in situ aberration-corrected transmission electron microscope (TEM) at high temperature. The twinned Pt₂Mo/C constitutes a promising CO-resistant catalyst for highly selective hydrogenation of nitroarenes. Theoretical calculations and environmental TEM suggest that the weakened CO adsorption over Pt sites of Pt₂Mo twin boundaries and their local region endows them with high CO resistance, selectivity, and reusability. The present strategy paves the way for tailoring the interface structure of high-melting point Mo/W-based intermetallic nanocrystals that proved to be important for the industrially viable reactions.