Direct Observation of Hollow Bimetallic Nanoparticle Formation through Galvanic Replacement and Etching Reactions

Hollow bimetallic nanoparticles (NPs) formed from metal oxide NP templates are widely used catalysts for hydrogen evolution and CO₂ reduction reactions. Despite their importance in catalysis, the details of how these NPs form on the NP templates remain unclear. Here, using in situ liquid-phase transmission electron microscopy (TEM) imaging, we describe the conversion of Cu₂O template NPs to hollow PdCu NPs. Our observations show that a polycrystalline PdCu shell forms on the surface of the template via a galvanic replacement reaction while the template undergoes anisotropic etching. This study provides important insights into the synthesis of hollow metallic nanostructures from metal oxide templates.