Chiral Plasmonic Printing of Discrete Hierarchical Chiral Au@Chiral Ag Semi‐Core‐Shell Nanorods With Chiral Plasmon‐Enhanced Photocatalysis

Understanding and harnessing the interaction between circularly polarized light (CPL) and nanocrystal morphology is crucial for designing advanced functional materials, yet a chemically chiral ligand-free pathway to fabricate structurally defined hybrid chiral nanostructures has been elusive. Herein, we report a novel chiral plasmonic printing strategy along with its underlying theoretical model, which employs the spin angular momentum of CPL as a chemically chiral-ligand-free stimulus to drive the asymmetric deposition of silver onto discrete chiral Au nanorods. This approach enables the programmable synthesis of hierarchically chiral Au@chiral Ag semi-core-shell nanostructures, whose chiroptical properties are synergistically governed by the intrinsic chirality of the Au core and the handedness of the incident CPL, and can be precisely modulated by illumination time. Theoretical modeling and experimental characterization jointly demonstrate that the chiral Ag shell dictates the circularly polarized photocatalytic activity performance via chiral hot-electron generation, as verified in the model reduction of 4-nitrophenol. This work not only establishes a versatile solution-phase route for fabricating complex chiral metallic nanostructures but also provides a predictive "light-handedness-to-nanostructure-to-function" framework, offering new opportunities for the rational design of advanced materials in asymmetric catalysis and chiral photonics.