Plasmon-driven photocatalytic molecular transformations on metallic nanostructure surfaces: mechanistic insights gained from plasmon-enhanced Raman spectroscopy

Optically excited plasmonic nanostructures exhibit unique capabilities to catalyze interfacial chemical transformations of molecules adsorbed on their surfaces in a regioselective manner through anomalous reaction pathways that are inaccessible under thermal conditions. The mechanistic complexity of plasmon-driven photocatalysis is intimately tied to a series of photophysical and photochemical processes associated with the radiative and non-radiative decay of localized plasmon resonances in metallic nanostructures. Plasmon-enhanced Raman spectroscopy combines ultrahigh detection sensitivity with unique time-resolving and molecular finger-printing capabilities, ideal for detailed kinetic and mechanistic studies of photocatalytic interfacial transformations of molecular adsorbates residing in the plasmonic hot spots. Through systematic case studies of several representative reactions, we demonstrate how plasmon-enhanced Raman spectroscopy can be judiciously utilized as a unique in situ spectroscopic tool to fine-resolve the detailed molecule-transforming processes on the surfaces of optically excited plasmonic nanostructures in real time during the photocatalytic reactions. We further epitomize the mechanistic insights gained from in situ plasmon-enhanced Raman spectroscopic measurements into several central materials design principles that can be employed to guide the rational optimization of the photocatalyst structures and the nanostructure-molecule interfaces for plasmon-mediated surface chemistry.