Plasmon-Driven Chemistry.

Plasmonic nanomaterials are promising photocatalysts due to their large optical cross sections and facile generation of nanoscale hotspot regions. They have been used to drive a range of photochemical reactions, including H dissociation, CO reduction, and ammonia synthesis, offering an exciting approach to light-driven chemistry. Deepening our understanding of how energy can be controllably transferred from the plasmonic nanomaterial to proximal reactants should lead to improvements in the efficiency and selectivity in plasmonic photocatalysis. Here we provide a comprehensive overview of plasmonic properties and explore different energy partitioning pathways. We focus on the importance of mapping molecular potential energy landscapes to understand reactivity and describe recent advancements in spectroscopic techniques, such as ultrafast surface-enhanced Raman spectroscopy, electron microscopy, and electrochemistry, that can aid in understanding how plasmonic nanomaterials can be used to shape potential energy surfaces and modify chemical outcomes. Additionally, we explore innovative hybrid plasmonic nanostructures such as antenna-reactor complexes, plasmonic single-atom catalysts, plasmonic picocavities, and chiral plasmonic substrates, all of which show great promise in advancing the field of plasmon-driven chemistry.