Ordered Intermetallic Nanoparticles with High Catalytic Activity Prepared by an Electrochemically Induced Phase Transformation

The synthesis of alloys with long range atomic scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in materials development. We report a process for converting colloidally synthesized ordered intermetallic PdBi₂ to ordered intermetallic Pd₃Bi nanoparticles under ambient conditions by an electrochemically induced phase transition. The low melting point of PdBi₂ corresponds to low vacancy formation energies which enables the facile removal of the Bi from the surface, while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd₃Bi exhibits 11x and 3.5x higher mass activty and high methanol tolerance for the oxygen reduction reaction compared to Pt/C and Pd/C, respectively,which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble metal rich ordered intermetallic phases with high catalytic activity, and sets forth guidelines for the design of ordered intermetallic compounds under ambient conditions.