Plasmonic metal nanostructures: concepts, challenges and opportunities in photo-mediated chemical transformations

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.