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Pd-based nanostructures with stepped facets possess potential applications in many fields, particularly in catalysis. Generally, crystal growth often only allows the formation of nanostructures with energetically non-stepped facets, so it is desirable to develop methods that can be used to prepare Pd-based nanostructures bounded by stepped facets. Herein, penta-fold twinned (PFT) Au@Pd nanobipyramids (NBs) with stepped {100} facets were synthesized through growing Pd on Au decahedral nanoparticles (NPs) in polyol. During the growth of Au@Pd NBs, Br− was a critical factor, because it has appropriate affinity for the Pd atom and adjusted the growth rate ratio along 〈110〉 and 〈100〉, resulting in the formation of Au@Pd NBs with stepped {100} facets. The product shape and size could be tailored by controlling the reaction conditions. Transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS), high angle annular dark field (HAADF) imaging and scanning transmission electron microscopy EDS (STEM-EDS) were used to investigate the structure and growth of the Au@Pd NBs. A growth mechanism involving two stages was elucidated. In the first stage, the growth of Pd clearly occurred along both 〈110〉 and 〈100〉. In the second stage, the growth along 〈110〉 was faster than that along 〈100〉. Furthermore, we also demonstrated that the as-prepared Au@Pd NBs had high catalytic activity, compared with Pd nanocubes and Pd–Au–Pd segmental nanorods.

Rational selection of halide ions for synthesizing highly active Au@Pd nanobipyramids