Nonepitaxial growth of uniform and precisely size-tunable core/shell nanoparticles and their enhanced plasmon-driven photocatalysis

Abstract

The ability to synthetically tune the size, shape, composition and architecture of inorganic nanostructures offers enormous opportunities to explore the fundamental structure–property relationships that occur uniquely at the nanoscale, and engineer greater functionality and design complexity into new material systems. Core/shell nanoparticles represent an important class of nanostructured materials that have garnered considerable interest. The success in producing core/shell nanoparticles with strictly controlled core diameter and shell thickness and tailoring their material properties relies crucially on the epitaxial growth of the shell material over the highly curved surface of the spherical core. However, effective methods to yield such high-quality core/shell nanoparticles are comparatively few and limited in scope. Here, we develop a robust nonepitaxial growth strategy to create uniform plasmonic/semiconducting core/shell nanoparticles with precisely controlled dimensions by capitalizing on amphiphilic star-like triblock copolymers as nanoreactors. The diameter of the plasmonic core and the thickness of the semiconductor shell can be independently and precisely regulated by tailoring the molecular weights (i.e., the lengths) of the inner and intermediate blocks of star-like triblock copolymers, respectively. The successful crafting of plasmonic/semiconducting core/shell nanoparticles was corroborated by the composition and structural characterizations. These functional nanoparticles exhibited largely improved photocatalytic activities, which can be attributed to the localized surface plasmon-mediated light harvesting enhancement of the plasmonic core and the built-in internal electric field. This nonepitaxial growth strategy offers new levels of tailorability in the dimensions, compositions and architectures of nanomaterials with engineered functionalities for applications in catalytic, electronic, optic, optoelectronic and sensory materials and devices.