Hot Electrons, Hot Holes, or Both? Tandem Synthesis of Imines Driven by the Plasmonic Excitation in Au/CeO Nanorods.

Solar-to-chemical conversion via photocatalysis is of paramount importance for a sustainable future. Thus, investigating the synergistic effects promoted by light in photocatalytic reactions is crucial. The tandem oxidative coupling of alcohols and amines is an attractive route to synthesize imines. Here, we unravel the performance and underlying reaction pathway in the visible-light-driven tandem oxidative coupling of benzyl alcohol and aniline employing Au/CeO nanorods as catalysts. We propose an alternative reaction pathway for this transformation that leads to improved efficiencies relative to individual CeO nanorods, in which the localized surface plasmon resonance (LSPR) excitation in Au nanoparticles (NPs) plays an important role. Our data suggests a synergism between the hot electrons and holes generated from the LSPR excitation in Au NPs. While the oxygen vacancies in CeO nanorods trap the hot electrons and facilitate their transfer to adsorbed O at surface vacancy sites, the hot holes in the Au NPs facilitate the α-H abstraction from the adsorbed benzyl alcohol, evolving into benzaldehyde, which then couples with aniline in the next step to yield the corresponding imine. Finally, cerium-coordinated superoxide species abstract hydrogen from the Au surface, regenerating the catalyst surface.