Plasmonic nanostructures have shown immense potential in photocatalysis because of their distinct photochemical properties associated with tunable photoresponses and strong light-matter interactions. The introduction of highly active sites is essential to fully exploit the potential of plasmonic nanostructures in photocatalysis, considering the inferior intrinsic activities of typical plasmonic metals. This review focuses on active site-engineered plasmonic nanostructures with enhanced photocatalytic performance, wherein the active sites are classified into four types (i.e., metallic sites, defect sites, ligand-grafted sites, and interface sites). The synergy between active sites and plasmonic nanostructures in photocatalysis is discussed in detail after briefly introducing the material synthesis and characterization methods. Active sites can promote the coupling of solar energy harvested by plasmonic metal to catalytic reactions in the form of local electromagnetic fields, hot carriers, and photothermal heating. Moreover, efficient energy coupling potentially regulates the reaction pathway by facilitating the excited state formation of reactants, changing the status of active sites, and creating additional active sites using photoexcited plasmonic metals. Afterward, the application of active site-engineered plasmonic nanostructures in emerging photocatalytic reactions is summarized. Finally, a summary and perspective of the existing challenges and future opportunities are presented. This review aims to deliver some insights into plasmonic photocatalysis from the perspective of active sites, expediting the discovery of high-performance plasmonic photocatalysts.
Keywords: active site engineering; design principle; emerging application; energy coupling; photocatalysis; plasmonic nanostructure; reaction pathway; synthesis and characterization.