Ag-Sn based system at nano size regime is one of the strongest candidates of lead-free solders. Besides, investigation of several other applications of Ag-Sn nanostructures, especially in catalysis, remains scarce...

Diluting the precious metal to be used for catalysis with an abundant and non‐precious metal to form alloy/intermetallic nanostructures is of great interest owing to the cost‐effectiveness of the catalyst. The physicochemical properties of such bimetallic nanostructures are influenced by the atomic ordering of different atoms in the system, generally enhancing the catalytic activity, selectivity, and durability compared to their monometallic counterparts. To understand the relationship between the structure and the activity of the catalyst, phase‐controlled synthesis of alloy/intermetallic nanostructures is crucial. Easy and scalable synthesis of such nanostructures with phase control presents a true challenge. We exploited a colloidal‐based synthetic route termed ‘co‐digestive ripening’ to prepare Pd−Sn alloy/intermetallic nanostructures. Oleylamine capped Pd and Sn colloids were utilized to obtain network‐like Pd3Sn and grape‐like Pd2Sn nanostructures. Temperature and the stoichiometric ratio between Pd and Sn played significant roles in achieving phase control. The mixture of ligands (oleylamine and trioctylphosphine) in the synthetic procedure resulted in the formation of well‐separated nanoparticles (2.9±0.5 nm) in the case of Pd3Sn and few nm‐sized particles along with aggregates in the case of Pd2Sn. Pd−Sn nanostructures showed enhanced activity and selectivity as compared to their monometallic counterparts for the catalytic performance towards oxidation of benzyl alcohol.