Surface Engineering of Spherical Metal Nanoparticles with Polymers toward Selective Asymmetric Synthesis of Nanobowls and Janus‐Type Dimers

New synthetic methods capable of controlling structural and compositional complexities of asymmetric nanoparticles (NPs) are very challenging but highly desired. A simple and general synthetic approach to designing sophisticated asymmetric NPs by anisotropically patterning the surface of isotropic metallic NPs with amphiphilic block copolymers (BCPs) is reported. The selective galvanic replacement and seed‐mediated growth of a second metal can be achieved on the exposed surface of metal NPs, resulting in the formation of nanobowls and Janus‐type metal–metal dimers, respectively. Using Ag and Au NPs tethered with amphiphilic block copolymers of poly(ethylene oxide)‐block‐polystyrene (PEO‐b‐PS), anisotropic surface patterning of metallic NPs (e.g., Ag and Au) is shown to be driven by thermodynamical phase segregation of BCP ligands on isotropic metal NPs. Two proof‐of‐concept experiments are given on, i) synthesis of Au nanobowls by a selective galvanic replacement reaction on Janus‐type patched Ag/polymer NPs; and ii) preparation of Au–Pd heterodimers and Au–Au homodimers by a seed‐mediated growth on Janus‐type patched Au/polymer NPs. The method shows remarkable versatility; and it can be easily handled in aqueous solution. This synthetic strategy stands out as the new methodology to design and synthesis asymmetric metal NPs with sophisticated topologies.