Exploiting Plasmonic Hot Spots in Au-Based Nanostructures for Sensing and Photocatalysis

ConspectusLocalized surface plasmon resonance is a unique property appearing in certain metal nanostructures, which can generate hot carriers (electrons and holes) and bring about an intense electromagnetic field localized near the surface of nanostructures. Specific locations, such as the rough surfaces and gaps in nanostructures, where a strong electromagnetic field is formed are referred to as hot spots. Hot-spot-containing plasmonic nanostructures have shown great promise in molecular sensing and plasmon-induced catalytic applications by exploiting the unique optical properties of hot spots. In this Account, we will review our recent developments in the synthesis of Au nanostructures consisting of multiple hot spots and Au-based heteronanostructures combining secondary active metals or semiconductors with Au nanostructures as promising plasmonic platforms for hot-spot-induced sensing and photocatalysis. We first provide a brief introduction to Au nanocrystals and Au nanoparticle assemblies with multiple hot spots. High-index-faceted hexoctahedral Au nanocrystals having multiple high-curvature vertices and edges are beneficial for the generation of an intense and reproducible electromagnetic field, which can enhance the performance of surface-enhanced Raman scattering-based molecular sensing. In addition, the engineering of interparticle gaps in Au nanoparticle assemblies to have a controlled size and a certain number of gaps can lead to the enhancement of plasmonic properties due to the significant amplification of the electromagnetic field at interparticle gaps. We then discuss hot-spot-containing Au-based heteronanostructures prepared by growing secondary components on the aforementioned Au nanostructures. With a combination of merit from strong plasmon energy formed by hot spots and catalytically active secondary materials, Au-based heteronanostructures have emerged as an attractive and versatile catalyst platform for various photocatalytic reactions. Through the control of key factors governing the photocatalysis of Au-based heteronanostructures, such as the coupling manner, shell thickness of secondary materials, and intimacy of contact, the plasmon energy formation of heteronanostructures and its transfer to catalytically active materials can be optimized, leading to the promotion of photocatalysis, such as photocatalytic hydrogen evolution. The rational design of Au nanostructures and Au-based heteronanostructures with multiple hot spots not only could realize enhanced sensing and photocatalysis but also could enable the understanding of the geometry-performance relationship. It is envisioned that the developed strategies can offer new opportunities for the design of various high-efficiency catalytic platforms.