One-step room-temperature synthesis of Au@Pd core–shell nanoparticles with tunable structure using plant tannin as reductant and stabilizer

Bayberry tannin (BT), a natural plant polyphenol, is used for the one-step synthesis of Au@Pd core–shell nanoparticles (Au@Pd NPs) in aqueous solution at room temperature. Due to its mild and stepwise reduction ability, BT was able to preferentially reduce Au3+ to Au NPs when placed in contact with an Au3+/Pd2+ mixture, and subsequently, the formed Au NPs served as in situ seeds for the growth of a Pd shell, resulting in the formation of Au@Pd NPs. Importantly, it is feasible to adjust the morphology of the Pd shell by varying the Pd2+/Au3+ molar ratio. Au@Pd NPs with a spherical Pd shell were formed when the Pd2+/Au3+ molar ratio was 1/50, while Au@Pd NPs with cubic Pd shell predominated when the ratio was increased to 2/1. The core–shell structure of synthesized Au@Pd NPs was characterized by TEM, HAADF-STEM, EDS mapping, an EDS line scan, and EDS point scan. Furthermore, density functional theory (DFT) calculations suggested that the localization of BT molecules on the surface of the Au clusters was the crucial factor for the formation of Au@Pd NPs, since the BT molecules increased the surface negative charges of the Au NPs, favoring the attraction of Pd2+ over Au NPs and resulting in the formation of a Pd shell.