Plasmonics: A Versatile Toolbox for Heterogeneous Photocatalysis

Plasmonic photocatalysis is a dynamic field of research devoted to the activation of chemical transformations thanks to the unique optoelectronic features of plasmonic nanomaterials such as their high electromagnetic field enhancements or their ability to generate nonthermalized charge carriers and localized temperature gradients. Importantly, the use of these objects as photocatalysts can lead to new reactivities when compared with classical heterogeneous photocatalysts, including an unprecedented control over efficiency and chemical selectivity within a broader range of the solar spectrum. In the present study, the most important aspects that need to be taken into consideration when designing a plasmonic photocatalytic system are summarized. Representative examples from the literature toward the rational design of the plasmonic photocatalyst are provided, together with a comprehensive list of organic and inorganic transformations that have been successfully modulated by plasmons. The importance of single nanoparticle measurements as a new means to characterize these systems is also discussed, allowing a better insight into single object heterogeneities or structure–function relationships that are usually lost in ensemble characterization techniques. Finally, the major role played by reaction intermediates when performing photoredox processes in solution is highlighted, particularly important when driving photochemical reactions in biological environments.