Plasmonic nanoparticles have recently emerged as promising photocatalysts for light-driven chemical conversions. Their illumination results in the generation of highly energetic charge carriers, elevated surface temperatures, and enhanced electromagnetic fields. Distinguishing between these often-overlapping processes is of paramount importance for the rational design of future plasmonic photocatalysts. However, the study of plasmon-driven chemical reactions is typically performed at the ensemble level and, therefore, is limited by the intrinsic heterogeneity of the catalysts. Here, we report an in situ single-particle study of a fluorogenic chemical reaction driven solely by plasmonic near-fields. Using super-resolution fluorescence microscopy, we map the position of individual product molecules with an ∼30 nm spatial resolution and demonstrate a clear correlation between the electric field distribution around individual nanoparticles and their super-resolved catalytic activity maps. Our results can be extended to systems with more complex electric field distributions, thereby guiding the design of future advanced photocatalysts.
Keywords: fluorogenic reactions; near-fields; photochemistry; plasmonics; super-resolution microscopy.