Crystal-Phase-Selective Etching of Heterophase Au Nanostructures

Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures. However, the synthesis of hollow multimetallic nanostructures based on crystal-phase-selective etching has been rarely studied. Here, a crystal-phase-selective etching method is reported to selectively etch the unconventional 4H and 2H phases in the heterophase Au nanostructures. Due to the coating of Pt-based alloy and the crystal-phase-selective etching of 4H-Au in 4H/face-centered cubic (fcc) Au nanowires, the well-defined ladder-like Au@PtAg nanoframes are prepared. In addition, the 2H-Au in the fcc-2H-fcc Au nanorods and 2H/fcc Au nanosheets can also be selectively etched using the same method. As a proof-of-concept application, the ladder-like Au@PtAg nanoframes are used for the electrocatalytic hydrogen evolution reaction (HER) in acidic media, showing excellent performance that is comparable to the commercial Pt/C catalyst.