Abstract
Plasmonic metal nanostructures (PMNs) are characterized by the plasmon oscillation of conduction band electron in response to external radiation, enabling strong light absorption and scattering capacities and near-field amplification. Owing to these enhanced light-matter interactions, PMNs have garnered extensive research interest in the past decades. Notably, a growingly large number of reports show that the energetics and kinetics of chemical transformations on PMNs can be modified upon photoexcitation of their plasmons, giving rise to a new paradigm of manipulating the reaction rate and selectivity of chemical reactions. On the other hand, there is urgent need to achieve clear understanding of the mechanism underlying the photo-mediated chemical transformations on PMNs for unleashing their full potential in converting solar energy to chemicals. In this perspective, we review current fundamental concepts of photo-mediated chemical transformations executed at PMNs. Three pivotal mechanistic questions, i.e., thermal and nonthermal effects, direct and indirect charge transfer processes, and the specific impacts of plasmon-induced potentials, are explored based on recent studies. We highlight the critical aspects in which major advancements should be made to facilitate the rational design and optimization of photo-mediated chemical transformations on PMNs in the future.