Glutathione-Mediated Synthesis of Yolk-Shell AuAg Nanostructures Containing a Spherical Core and Cuboctahedral Skeletons and Their Applications in Plasmonic Catalysis.

Frame/skeleton-like nanostructures are of great value in plasmonic catalysis as a result of the synergetic structural advantages arising from both maximized surface atomic exposure and efficient incident light absorptions. Herein, we report the size-tunable fabrication of yolk-shell AuAg nanoparticles containing a spherical core and cuboctahedral skeletons (AuAg YSCNSs), together with the exploration of their applications for assisting the reduction of 4-nitrophenol (4-NP) under ultraviolet-visible (UV-vis) light irradiation. The use of glutathione (GSH) at an appropriate amount to mediate the galvanic replacement reaction between Au@Ag core-shell nanocubes and HAuCl is found to be crucial in regulating the shape evolution. Their sizes could be readily tuned by altering the edge lengths of Au@Ag core-shell nanocubes. When working as the photocatalyst assisting the reduction of 4-NP, the AuAg YSCNSs exhibit a higher apparent rate constant under UV-vis light irradiation. The current work demonstrates the feasibility to create skeleton-like noble metal nanocrystals with the shape largely deviated from that of the original template via the "top-down" carving strategy by introducing non-metallic surface doping, which could be potentially extended to other noble metals or alloys.