Alloying bulk-immiscible metals at the nanoscale: An XPS/STM study of bimetallic Ag-Pt/HOPG nanoparticles

The intentional tailoring of surface structure in bimetallic nanoparticles is of high interest for academic research and industry, and many attempts have been made to improve the control over the distribution mode of the constituent elements which ranges from homogeneously mixed nanoalloys to core-shell nanostructures. However, some metal combinations exhibit a wide miscibility gap in the bulk, which nonetheless could be overcome under definite conditions at the nanoscale due to size effects. Here we present the detailed XPS/STM investigation of alloying capability of bulk-immiscible metals on the example of the Ag-Pt/HOPG bimetallic system prepared by thermal vacuum deposition. We found out that partial alloying of Ag and Pt occurs already at the preparation stage, and the following thermal annealing of the Ag-Pt/HOPG samples at 300-400 degrees C does not help to enhance the alloying degree owing to thermodynamically driven surface segregation of silver. Increasing the annealing temperature ruins the structure of Ag-Pt bimetallic nanoparticles due to silver sublimation, while even longer annealing time leads to partial phase separation. Our results demonstrate a limited alloying capability of Pt and Ag at the nanoscale which will be relevant for further research on the design and functioning of bimetallic catalysts containing bulk-immiscible metals.