Cu²⁺–Assisted Synthesis of Ultrasharp and Sub-10 nm Gold Nanostars. Applications in Catalysis, Sensing, and Photothermia

Gold nanostars have shown enormous potential as the main enablers of advanced applications ranging from biomedicine to sensing or catalysis. Their unique anisotropic structure featuring sharp spikes that grow from a central core offers enhanced optical capabilities and spectral tunability. Although several synthesis methods yield NSs of different morphologies and sizes up to several hundred nanometers, obtaining small NSs, while maintaining their plasmonic properties in the near-infrared, has proven challenging and elusive. Here, we show that Cu²⁺ addition during NS synthesis in polyvinylpyrrolidone/dimethylformamide generates more crystallographic defects and promotes the directional growth, giving rise to NSs with a larger number of much sharper spikes. They are also formed at smaller volumes, enabling the generation of ultrasmall nanostars, with a volume as small as 421 nm³ (i.e., 9.2 nm of volume-equivalent diameter), while maintaining a plasmon resonance in the near-infrared. To this end, we systematically evaluate the influence of synthesis parameters on the nanostar size and optical characteristics and demonstrate their properties for applications in catalysis, surface-enhanced Raman spectroscopy sensing, and hyperthermia. The ultrasmall nanostars show excellent attributes in all of them, leveraging their small size to enhance properties related to a higher surface-to-volume ratio or colloidal diffusivity.