Interfacial Hot Carrier Accumulation in Plasmon Photocatalysis

ABSTRACT Plasmonic photocatalysts play a central role in heterogeneous photocatalysis. However, the highly energetic hot carriers (electrons and holes) generated via plasmon non‐radiative decay suffer from ultrashort lifetimes on the femtosecond and picosecond scale. This rapid relaxation severely limits their ability to participate in most conventional reactions. Therefore, prolonging the lifespan of hot carriers by separating and localizing them at specific active sites is necessary. This review focuses on recent strategies designed to trap and accumulate hot carriers to enhance their efficient extraction and utilization. We systemically discuss fundamental approaches, including constructing metal‐semiconductor Schottky heterojunctions, engineering heterometallic structures, functionalizing metal nanoparticles with surface molecules, and applying external stimuli. Furthermore, we highlight how the localized accumulation of hot carriers enables multi‐carrier collaboration catalysis and highly selective product generation. Finally, the current challenges and future prospects of hot carrier accumulation in plasmonic photocatalysis are discussed as well.