Freestanding Penta-Twinned Pd–Ag Nanosheets

2D metal nanosheets have attracted significant attention as efficient catalysts for various important chemical reactions. However, the development of metal nanosheets with controlled compositions and morphologies has been slow due to the challenges associated with synthesizing thermodynamically unfavorable 2D structures. Herein, we report a synthesis route of freestanding Pd-Ag penta-twinned nanosheets (Pd-Ag ptNSs) with distinct 5-fold twin boundaries. Through the coreduction of Ag and Pd precursors on presynthesized Pd ptNSs, Ag could be homogeneously alloyed with Pd, leading to the formation of well-defined Pd-Ag ptNSs. The promotional effects of the bimetallic composition, 2D structure, and twin boundaries on catalysis were studied by using Pd-Ag ptNS-catalyzed H₂ production from formic acid decomposition as a model reaction. Notably, the catalytic activity of the Pd-Ag ptNSs drastically outperformed those of monometallic, bimetallic, and 3D counterparts, such as Pd ptNSs, Pd-Ag nanosheets without a TB, and Pd-Ag octahedral nanocrystals, demonstrating the promising potential of the integration of twin boundaries and multiple compositions in the development of high-performance 2D nanocatalysts.