Chiral Au@Semiconductor Yolk–Shell Nanostructures with Tailored Chiroptical Properties and Chirality‐Dependent Photocatalysis

ABSTRACT The spatial configuration of chiral metal‐semiconductor hybrid nanostructures directly determines the coupling efficiency between chiral plasmonic metals and semiconductors, which in turn affects their key physical and chemical properties and applications in diverse scenarios. However, precise spatial control of complex chiral hybrid nanostructures with increased structural and compositional diversity remains a significant challenge. Herein, we develop a general bottom‐up synthetic strategy for the construction of chiral Au@semiconductor yolk–shell nanostructures. By using chiral Au@Cu 2 O nanostructures with tunable geometric parameters as a chiral core, a finely controlled redox‐coupled ion exchange process is employed to realize the transition from a Cu 2 O shell to other semiconductors, including Cu 7 S 4 , Cu 2‐x Se, CdS, and CuFeS 2 , to form chiral Au@semiconductor yolk–shell structures. More importantly, intriguing shell‐dependent chiroptical activities were experimentally observed and further elucidated by the theoretical simulations. The controllable integration of chiral plasmonic nanostructures with semiconductor components further allows applications in chirality‐dependent photocatalysis. The insights gained from this work provide an important knowledge framework for understanding the coupling of the semiconductor shell with the chiral plasmonic core that underpins the design of multifunctional chiral hybrid plasmonic nanomaterials toward catalysis and photonics.