Intermediate Structures of Pt–Ni Nanoparticles during Selective Chemical and Electrochemical Etching

Both chemical and electrochemical etching are effective methods for tailoring the surface composition of Pt-based catalytic bimetallic nanoparticles (NPs). However, the detailed nanoscale etching mechanisms, which are needed for achieving fine control over the etch processes, are still not understood. Here, we study selective chemical and electrochemical Ni etching of Pt–Ni rhombic dodecahedron NPs using in situ liquid-phase transmission electron microscopy. Our real-time observations show that the intermediate NP structures evolve differently in the two cases. Chemical etching of Ni starts from localized pits on the NP surface, in contrast to the uniform dissolution of Ni during the electrochemical etching. Our study reveals how oxidative etching participates in the removal of a non-noble metal and the subsequent formation of noble-metal-rich NPs. The mechanistic insights reported here highlight the role of a native surface oxide layer on the etching behavior, which is important for the design of NPs with specific surface composition for applications in electrocatalysis.