The catalytic properties of noble metal nanocrystals can be tuned via engineering their structures. Nanocrystals with fractal structures are fascinating catalysts regarding their large surface area-to-volume ratios, large numbers of edges and corners, which can be tuned simultaneously by their hierarchical ordering. However, it is still a great challenge to control the hierarchical ordering of noble metal fractal nanocrystals and their formation mechanism is not fully understood. Herein, we report a facile solvothermal method for the direct preparation of a unique single-crystal Rh-hyperbranched structure, which consists of hierarchically ultrathin nanoplates with threefold symmetry, large surface area and high density of low-coordinated edge/corner sites. Importantly, the hierarchical ordering can be readily tuned by changing the composition of solvent. In addition, we found the as-prepared single-crystal hyperbranched Rh nanoplates possessed great structure stability, and exhibited better catalytic performance towards both ethanol electrooxidation and hydrogenation of styrene than the commercial Rh black, which can be attributed to the large surface area and high-dentisty of edge/corner sites.
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