Metallic nanoparticle-based photocatalysts have gained a lot of interest in catalyzing oxidation–reduction reactions. In previous studies, the poor performance of these catalysts is partly due to their operation that relies on picosecond-lifetime hot carriers. In this work, electrons that accumulate at a photostationary state, generated by photocharging the catalysts, have a much longer lifetime for catalysis. This approach makes it possible to determine and tune the photoredox potentials of the catalysts. As demonstrated in a model reaction, the photostationary state of the photocatalyzed oxidative etching of colloidal gold nanoparticles using FeCl3 was established under continuous irradiation of different wavelengths. The photoredox potentials of the nanoparticles were then calculated using the Nernst equation. The potentials can be tuned to a range of 1.28 to 1.40 V (vs SHE) under irradiation of different wavelengths in the range of 450 to 517 nm. The effects of particle size or optical power on the photoredox potentials are small compared to the wavelength effect. Control over the photoredox potential of the particles using different excitation wavelengths can potentially be used to tune the activities and selectivities of metallic nanoparticle photocatalysts.

Summary Utilizing 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 the d -band catalyze the oxidative addition of aryl halide R-X onto Pd 0 at the nanoparticles' surface to form R-Pd II -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.

Photocatalysis induced by localized surface plasmon resonance of metallic nanoparticles has been studied for more than a decade, but photocatalysis originating from direct interband excitations is still under-explored. The spectral overlap and the coupling of these two optical regimes also complicate the determination of hot carriers' energy states and eventually hinder the accurate assignment of their catalytic role in studied reactions. In this Featured Article, after reviewing previous studies, we suggest classifying the photoexcitation via intra-and interband transitions where the physical states of hot carriers are well-defined. Intraband transitions are featured by creating hot electrons above the Fermi level and suitable for reductive catalytic pathways, whereas interband transitions are featured by generating hot d-band holes below the Fermi level and better for oxidative catalytic pathways. Since the contribution of intra-and interband transitions are different in the spectral regions of localized surface plasmon resonance and direct interband excitations, the wavelength dependence of the photocatalytic activities is very helpful in assigning which transitions and carriers contribute to the observed catalysis.

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Photocatalysis of metallic nanoparticles, especially utilizing hot electrons generated from localized surface plasmon resonance, is of widespread interest. However, the role of hot holes, especially generated from interband transitions, has not been emphasized in exploring the photocatalytic mechanism yet. In this study, a photocatalyzed Suzuki-Miyaura reaction using mesoporous Pd nanoparticle photocatalyst served as a model reaction to study the role of hot holes by accurately measuring the quantum yields of the photocatalyst. The quantum yields increase under shorter wavelength excitations and correlate to the “deeper” energy of the holes from the Fermi level. Our mechanistic study suggests that deeper holes in the d-band can catalyze the oxidative addition of aryl halide R-X onto Pd0 at the surface of nanoparticles to form the R-PdII-X complex, the rate-determining step of the established catalytic cycle. We pointed out that this deep hole mechanism should deserve as much attention as the well-known hot electron transfer mechanism in previous studies.