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A simple one-pot approach to the in situ construction of ultrathin shells is developed to create a new highly efficient and durable Pt-based electrocatalyst for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Herein, the synthesized ultrathin PdPtAg-shells are located on twinned PdAg nanocrystals and deposited onto graphene (G) (denoted by PdAg@PdPtAg/rGO). The PdAg@PdPtAg/rGO nanocrystal shows a low overpotential of 22 mV at 10 mA cm−2 and excellent electrochemical stability with 99.5% retention over either 12 h or 30 000 cycles of HER. Meanwhile, its ORR activities in acidic and alkaline media are very high and better than that of commercially available Pt/C. Both the experimental and calculated results suggest that the presence of an ultrathin PdPtAg alloy shell synthesized on a PdAg twinned support is the main reason for the greatly enhanced activities. Moreover, the twinned PdAg nanocrystal provides a number of twinned grain boundaries and defect sites (such as step, edge and kink sites). This typical structure represents a new strategy for synthesizing high-performance Pt-based catalysts, promoting their practical applications in energy conversion and storage devices.

Surface ion vacancy engineering at the atomic scale has attracted much attention to efficiently improve the electrocatalytic activity for the hydrogen evolution reaction (HER). Especially, compared with anion vacancies, cation vacancies are more challenging to generate, and studies on the structure–activity relationship of ion vacancy-rich metal oxide catalysts are still lacking. Herein, by means of abundant dangling unsaturated O and Ru vacancies, we report atomically dispersed MoRu pairs (rGO-MoO3−x–MoRu) stabilized with well-coupled graphene and MoO3−x. The atomically dispersed state of MoRu sites is confirmed by both high-angle annular dark-field scanning TEM (HAADF-STEM) and X-ray absorption fine structure (XAFS) measurements. As a result, rGO-MoO3−x–MoRu pairs show outstanding HER performance with very low overpotentials of 20 and 60 mV at 10 mA cm−2 under alkaline and acidic conditions, and maintain steady hydrogen bubble evolution continuously for 35 h. Meanwhile, for HER activity, they exhibit a positive correlation with the amount of oxygen vacancies, resulting in a favorable change in the adsorption behavior of H atoms on their neighboring Mo or Ru atoms.