Rh@Au Core–Shell Nanocrystals with the Core in Tensile Strain and the Shell in Compressive Strain

Bimetallic nanocrystals provide a versatile platform for utilizing the desired characteristics of two different elements within one particle. Core–shell nanocrystals, in particular, have found widespread use in catalysis by providing an ability to leverage the strains arising from the lattice mismatch between the core and the shell. However, large (>5%) lattice mismatch tends to result in nonepitaxial growth and lattice defects in an effort to release the strain. Herein, we report the epitaxial growth of Au on Rh cubic seeds under mild reaction conditions to generate Rh@Au truncated octahedra featuring a lattice mismatch of 7.2%. Key to the success was the use of small (4.5 nm) Rh cubes as seeds, which could homogeneously distribute the tensile strain arising from the epitaxial growth of a conformal, compressively strained Au shell. Further, delicate tuning of kinetic parameters through the introduction of NaOH and KBr into the synthesis allowed for a unique nucleation pattern that led to centrally located cores and a narrow size distribution for the product. A thorough investigation of the various possible highly strained morphologies was conducted to gain a full understanding of the system.