The hollow noble metal nanostructures have attracted wide attention in catalysis/electrocatalysis. Here a two-step procedure for constructing hollow Rh nanospheres (Rh H-NSs) with clean surface is described. By selectively removing the surfactant and Au core of Au-core@Rh-shell nanostructures (Au@Rh NSs), the surface-cleaned Rh H-NSs are obtained, which contain abundant porous channels and large specific surface area. The as-prepared Rh H-NSs exhibit enhanced inherent activity for the methanol oxidation reaction (MOR) compared to state-of-the-art Pt nanoparticles in alkaline media. Further electrochemical experiments show that Rh H-NSs also have high activity for the electrooxidation of formaldehyde and formate (intermediate species in the course of the MOR) in alkaline media. Unfortunately, Rh H-NSs have low electrocatalytic activity for the ethanol and 1-propanol oxidation reactions in alkaline media. All electrochemical results indicate that the order of electrocatalytic activity of Rh H-NSs for alcohol oxidation reaction is methanol (C<sub>1</sub> ) > ethanol (C<sub>2</sub> ) > 1-propanol (C<sub>3</sub> ). This work highlights the synthesis route of Rh hollow nanostructures, and indicates the promising application of Rh nanostructures in alkaline direct methanol fuel cells.
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