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Simultaneously growing multiple nanocrystallites in a crowded space can cause a shortage of precursors, and this can lead to a vertical growth of nanocrystallites on a given substrate. The presence of surfactant-surfactant interactions among adjacent nanocrystals can also place a unique structural constraint on the growing nanocrystallites, resulting in novel nanocrystal facet control. Herein, we report the growth of Rh on Au@Pt nanowires with multiple twinning boundaries, which are found along the entire nanowire length. The Au@Pt nanowires exhibit numerous bead-like structures, resulting from the preferred Pt deposition on the twinning boundaries, which can serve as nucleation sites for Rh. The heteroepitaxial growth of Rh on the Au@Pt nanowires results in unusual crystal growth behaviours. First, novel morphologies of Rh nanorods, nanoplates, and tangled manes are obtained temperature-dependently, which are not obtained in the absence of the Au@Pt nanowire substrate. Secondly, the thickness of vertically grown nanorods and nanoplates is tightly controlled. We also report the structure-catalytic activity relationship on the catalytic hydrogenation of phthalimides by the new Rh nanostructures.

Surface-energy fine-tuned five-fold twinned nanostructures with a core-shell Pt3Ni@Rh structural motif, namely, a core-shell Pt3Ni@Rh pentagon, a core-shell Pt3Ni@Rh starfish, and a paddlewheel with a Pt3Ni crankshaft and two Rh five-fold starfish wheels, are prepared by rationally designed stepwise heteroepitaxial growth. Unusual selective hydrogenation of the phenyl ring in phthalimide is accomplished with moderately active core-shell Pt3Ni@Rh pentagons and starfish-like nanoparticles. The most active paddlewheel structure proceeds to further reduce one carbonyl group, indicating the sequential nature of phthalimide reduction by Rh nanoparticle catalysis.

Facet-controlled dendritic nanostructures are expected to exhibit excellent catalytic properties because both aggregation-free nature and controlled facet-originated activity and selectivity can be accomplished. However, such examples are extremely rare due to the incompatibility of the dendrite formation process with the usage of surface-stabilizing moieties, which are typically used to control facets. Herein, we demonstrate that regiospecific growth on a facet-controlled core nanoparticle can induce the facet-control of the branch nanoparticles. Specifically, facet-controlled dendritic nanostructures of {100}Rh–Pt and {100}Pt–Pt can be conveniently prepared by transferring the crystallographic behaviour of the {100}Pt dendritic core nanocube to the {100}Rh or {100}Pt branch nanocubes.

Impurity doping has yielded a number of useful optical and catalytic alloy nanoparticles, by providing synthetic routes to unprecedented nanostructures. However, Zn is difficult to use as a dopant in alloy nanoparticles due to the difficulty in reduction, and therefore little has been reported on Zn-doped alloy nanoparticles and their potential applications. Herein we report an unusual role of the dopant Zn as a crystal growth modifying agent to cause the formation of novel concave Rh nanostructures, namely nanotents. We could further prepare unprecedented hierarchically stacked Rh nanoframes and dendritic nanostructures derived from them by understanding the role of various surface-stabilizing moieties. We also report the usage of new Rh nanostructures in selective hydrogenation of phthalimides.