Plasmonic Dodecahedral‐Walled Elongated Nanoframes for Surface‐Enhanced Raman Spectroscopy

Abstract Here, elongated pseudohollow nanoframes composed of four rectangular plates enclosing the sides and two open‐frame ends with four ridges pointing at the tips for near‐field focusing are reported. The side facets act as light‐collecting domains and transfer the collected light to the sharp tips for near‐field focusing. The nanoframes are hollow inside, allowing the gaseous analyte to penetrate through the entire architecture and enabling efficient detection of gaseous analytes when combined with Raman spectroscopy. The resulting nanostructures are named Au dodecahedral‐walled nanoframes. Synthesis of the nanoframes involves shape transformation of Au nanorods with round tips to produce Au‐elongated dodecahedra, followed by facet‐selective Pt growth, etching of the inner Au, and regrowth steps. The close‐packed assembly of Au dodecahedral‐walled nanoframes exhibits an attomolar limit of detection toward benzenethiol. This significant enhancement in SERS is attributed to the presence of a flat solid terrace for a large surface area, sharp edges and vertices for strong electromagnetic near‐field collection, and open frames for effective analyte transport and capture. Moreover, nanoframes are applied to detect chemical warfare agents, specifically mustard gas simulants, and 20 times higher sensitivity is achieved compared to their solid counterparts.