Hairy Uniform Permanently Ligated Hollow Nanoparticles with Precise Dimension Control and Tunable Optical Properties

The ability to tailor the size and shape of nanoparticles (NPs) enables the investigation into the correlation between these parameters and optical, optoelectronic, electrical, magnetic, and catalytic properties. Despite several effective approaches available to synthesize NPs with a hollow interior, it remains challenging to have a general strategy for creating a wide diversity of high-quality hollow NPs with different dimensions and compositions on demand. Herein, we report on a general and robust strategy to in situ crafting of monodisperse hairy hollow noble metal NPs by capitalizing on rationally designed amphiphilic star-like triblock copolymers as nanoreactors. The intermediate blocks of star-like triblock copolymers can associate with metal precursors via strong interaction (i.e., direct coordination or electrostatic interaction), followed by reduction to yield hollow noble metal NPs. Notably, the outer blocks of star-like triblock copolymers function as ligands that intimately and permanently passivate the surface of hollow noble metal NPs (i.e., forming hairy permanently ligated hollow NPs with superior solubility in nonpolar solvents). More importantly, the diameter of the hollow interior and the thickness of the shell of NPs can be readily controlled. As such, the dimension-dependent optical properties of hollow NPs are scrutinized by combining experimental studies and theoretical modeling. The dye encapsulation/release studies indicated that hollow NPs may be utilized as attractive guest molecule nanocarriers. As the diversity of precursors are amenable to this star-like triblock copolymer nanoreactor strategy, it can conceptually be extended to produce a rich variety of hairy hollow NPs with different dimensions and functionalities for applications in catalysis, water purification, optical devices, lightweight fillers, and energy conversion and storage.