摘要：SummaryUtilizing hot electrons generated from localized surface plasmon resonance is of widespread interest in the photocatalysis of metallic nanoparticles. However, hot holes, especially generated from interband transitions, have not been fully explored for photocatalysis yet. In this study, a photocatalyzed Suzuki-Miyaura reaction using mesoporous Pd nanoparticle photocatalyst served as a model to study the role of hot holes. Quantum yields of the photocatalysts increase under shorter wavelength excitations and correlate to “deeper” energy of the holes from the Fermi level. This work suggests that deeper holes in thed-band catalyze the oxidative addition of aryl halide R-X onto Pd0at the nanoparticles' surface to form R-PdII-X complex, thus accelerating the rate-determining step of the catalytic cycle. The hot electrons do not play a decisive role. In the future, catalytic mechanisms induced by deep holes should deserve as much attention as the well-known hot electron transfer mechanism.Graphical abstractDisplay OmittedHighlights•Comparison of quantum yield across different wavelengths•Interband transitions from shorter wavelength excitation offering deeper holes•Deeper holes with stronger oxidizing power for higher quantum yieldChemistry; Catalysis; Materials science
