Chemically modified nanofoci unifying plasmonics and catalysis.

A plasmonic nanofocus, often in the form of a nanogap, is capable of concentrating light in a nanometric volume. The greatly enhanced electromagnetic field offers many opportunities in physics and chemistry. However, the lack of a method to fine-tune the chemical activities of the nanofocus has severely limited its application. Here we communicate an intriguing class of chemically modified nanofoci (CMNFs) that are able to address this challenge. Our results successfully demonstrate a possibility to functionalize the nanosized, mass-transport-restricted nanogap (nanofocus) of a dimeric gold nanoparticle assembly with homo-(Au) and heterogeneous (Ag, Pt, and Pd) materials. The as-produced structures with conductive Au and Ag junctions generate a novel form of charge transfer plasmon (CTP) with continuously tunable frequency covering the visible and near-infrared domains. In addition, the Ag materials can be displaced by catalytic Pt and Pd metals while still maintaining a tightly focused electromagnetic field. These hybrid structures with unified catalytic and plasmonic properties enable real-time, on-site probing of catalytic conversions at the nanofocus by plasmon-enhanced Raman scattering. The chemically/optically engineered CMNFs represent the simplest function-integrated nanodevices for plasmonics, sensing, and catalysis. Our work not only realizes chemical CTP reshaping, but also allows chemical functionalization into an intensified plasmonic near-field. The latter may enable unconventional chemical reactions driven by the catalytically functionalized, strongly boosted light field.