Monitoring plasmonic hot-carrier chemical reactions at the single particle level

摘要： Plasmon excitation in metal nanoparticles triggers the generation of highly energetic charge carriers that - properly manipulated and exploited - can mediate chemical reactions. Single-particle techniques are key to unearth the underlying mechanisms of hot-carrier generation, transport and injection as well as to disentangle the role of the temperature increase and the enhanced near-field at the nanoparticle-molecule interface. Gaining a nanoscopic insight of these processes and their interplay could aid in the rational design of plasmonic photocatalysts. Here, we present three different approaches to monitor hot-carrier reactivity at the single-particle level. We use a combination of dark-field microscopy and photo-electrochemistry to track a hot-hole driven reaction on a single Au nanoparticle. We image hot-electron reactivity with sub-particle spatial resolution using nanoscopy techniques. Finally, we push the limits looking for a hot-electron induced chemical reaction that generates a fluorescent product, which should enable imaging of active plasmonic photocatalysis at the single-particle and single-molecule levels.