Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Kontoleta, Evgenia; Tsoukala, Alexandra; Askes, Sven H. C.; Zoethout, E.; Oksenberg, Eitan; Agrawal, Harshal; Garnett, Erik C.

doi:10.1021/acsami.0c04941

Cited by 16 publications

(17 citation statements)

References 68 publications

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“…X‐ray diffraction (XRD) patterns were measured with a Bruker D2 Phaser with Cu K α radiation (λ = 1.5406 Å). Atomic layer deposition (ALD) of alumina was performed with a previously published procedure at 250 °C, [ 76 ] resulting in a thickness of exactly 10.0 nm. All data and images were further processed using Microsoft Excel, Origin 2017, and ImageJ 2.0 software.…”

Section: Methodsmentioning

confidence: 99%

Ultrafast Photoinduced Heat Generation by Plasmonic HfN Nanoparticles

O'Neill

Frehan

Zhu

et al. 2021

Advanced Optical Materials

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carrier generation. [1,2] This has led to sig nificant interest in plasmonic nanostruc tures for photocatalysis, either through local heat generation or as a photo sensitizer. [3,4] Materials in the family of plasmonic transition metal nitrides (e.g., TiN, HfN, NbN, WN) feature high ther momechanical robustness and recently have been proposed for applications requiring extreme operating conditions, such as photothermal catalysis or solar thermophoto voltaics. [5] These materials have high melting points and demonstrate high temperature durability, chemical sta bility, and corrosion resistance, while pre senting an optical response similar to Au or Ag plasmonic nanostructures. [5,6] With a strong response in the visible range, high mechanical hardness, low material cost, [6][7][8][9] and outstanding performance in electro chemical reactions, [10][11][12] the photophysics of these materials requires further research. In the following, we will briefly review the current level of understanding of the photophysics of noble metal plasmonic particles, followed by a discussion on transition metal nitride plasmonic nanoparticles.Light absorption and heat generation by noble metal nano particles can be summarized as follows: first, the local surface plasmon resonance (LSPR) is excited, which lasts several fs and decays by nonradiative dephasing through Landau damp ening (1-100 fs). This process generates hot carriers at regions with high optical absorption (hotspots), the hot carriers subse quently decay by electron-electron scattering (1-100 fs) followed by electron-phonon coupling (0.1-10 ps). Ultimately, phonons dissipate heat to the surroundings (1-10 ns). [4,13,14] There is increasing interest in hot carrier processes, chemical reac tions induced by them, and determining whether the observed changes in chemical reactions are due to lattice heating or hot charge carriers. [15,16] Since elementary chemical transformations typically occur on a 1-100 ps timescale, [17] it is essential to characterize the light induced carrier dynamics and thermal relaxation of plasmonic systems that consist of nonnoble metal materials. Recent studies have shown that in particular hafnium nitride (HfN) performs well at converting light into heat through thermoplas monic relaxation. [18,19] This efficient lightinduced heating likely stems from a less negative real permittivity (ε′) and a higher imaginary permittivity (ε″) of HfN relative to noble metals, leading to a lossy plasmonic response accompanied by lower There is great interest in the development of alternatives to noble metals for plasmonic nanostructures. Transition metal nitrides are promising due to their robust refractory properties. However, the photophysics of these nanostructures, particularly the hot carrier dynamics and photothermal response on ultrafast timescales, are not well understood. This limits their implementation in applications such as photothermal catalysis or solar thermophotovoltaics. In this study, the light-induced relaxation processes in water-dispersed Hf...

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Section: Methodsmentioning

confidence: 99%

Ultrafast Photoinduced Heat Generation by Plasmonic HfN Nanoparticles

O'Neill

Frehan

Zhu

et al. 2021

Advanced Optical Materials

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“…Among the processes that can be driven by the excitation of plasmonic hot carriers, some can change the plasmonic NC itself, as schematically depicted in Figure b. These include growth by aggregation of metal ions, ,− shrinkage by photoetching, , and growth or accretion of other materials on its surface. − The schematic diagram in Figure b illustrates the fundamental idea behind the HE-directed metal growth, which will depend on the local rate of HE injection and leads to locally induced growth, changing the NC’s shape. This picture of inhomogeneous HE-directed growth contrasts, for instance, with the resulting surface pattern expected from both growth and surface reactions , driven by photoheating.…”

Section: Photoinduced Growth and Chiralitymentioning

confidence: 99%

Local Growth Mediated by Plasmonic Hot Carriers: Chirality from Achiral Nanocrystals Using Circularly Polarized Light

et al. 2021

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Plasmonic nanocrystals and their assemblies are excellent tools to create functional systems, including systems with strong chiral optical responses. Here we study the possibility of growing chiral plasmonic nanocrystals from strictly nonchiral seeds of different types by using circularly polarized light as the chirality-inducing mechanism. We present a novel theoretical methodology that simulates realistic nonlinear and inhomogeneous photogrowth processes in plasmonic nanocrystals, mediated by the excitation of hot carriers that can drive surface chemistry. We show the strongly anisotropic and chiral growth of oriented nanocrystals with lowered symmetry, with the striking feature that such chiral growth can appear even for nanocrystals with subwavelength sizes. Furthermore, we show that the chiral growth of nanocrystals in solution is fundamentally challenging. This work explores new ways of growing monolithic chiral plasmonic nanostructures and can be useful for the development of plasmonic photocatalysis and fabrication technologies.

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“…This catalytic mechanism has been demonstrated in many reductive reactions, such as reduction of CO 2 or nitro compounds ( Gellé et al., 2020 ; Zhang et al., 2018 ). Recently, the hot holes could also be utilized for some oxidative reactions, such as alcohol oxidation ( Boltersdorf et al., 2018 ; Kontoleta et al., 2020 ; Zhang et al., 2020 ; Zhu et al., 2009 ). On the other hand, interband transitions, generating “deeper” holes below E F and electrons near E F , are more suitable for the oxidative pathway where the nanoparticle photocatalysts are better used for hole-mediated oxidation reactions.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic insight into deep holes from interband transitions in Palladium nanoparticle photocatalysts

et al. 2022

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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.

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Using Hot Electrons and Hot Holes for Simultaneous Cocatalyst Deposition on Plasmonic Nanostructures

Cited by 16 publications

References 68 publications

Ultrafast Photoinduced Heat Generation by Plasmonic HfN Nanoparticles

Ultrafast Photoinduced Heat Generation by Plasmonic HfN Nanoparticles

Local Growth Mediated by Plasmonic Hot Carriers: Chirality from Achiral Nanocrystals Using Circularly Polarized Light

Mechanistic insight into deep holes from interband transitions in Palladium nanoparticle photocatalysts

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