Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters

Douglas-Gallardo, Oscar A.; Box, Connor L.; Maurer, Reinhard J.

doi:10.1039/d1nr02033a

Cited by 13 publications

(6 citation statements)

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“…Hydrogenation of these stabilized intermediates subsequently desorb as CH 3 OH. Thus, the strong detection of H 3 CO* intermediates on the illuminated metasurface in our DRIFTS measurement may be evidence for active hydrogenation, where hydrogen dissociation on metallic nanoparticles have been shown to be favorable due to indirect charge transfer. − Noticeably the absorption peaks associated with copper are mostly unobserved in the metasurface IR spectrum. This may be linked to the high Drude conductivity of the Au back mirror, which results in high reflectivity across the infrared spectrum.…”

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confidence: 80%

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation

et al. 2021

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Metamaterials are a new class of artificial materials that can achieve electromagnetic properties that do not occur naturally, and as such they can also be a new class of photocatalytic structures. We show that metal-based catalysts can achieve electromagnetic field amplification and broadband absorption by decoupling optical properties from the material composition as exemplified with a ZnO/Cu metamaterial surface comprising periodically arranged nanocubes. Through refractive index engineering close to the index of air, the metamaterial exhibits nearperfect 98% absorption. The combination of plasmonics and broadband absorption elevates the weak electric field intensities across the nonplasmonic absorption range. This feedback between optical excitation and plasmonic excitation dramatically enhances light-to-dark catalytic rates by up to a factor of 181 times, compared to a 3 times photoenhancement of ZnO/Cu nanoparticles or films, and with angular invariance. These results show that metamaterial catalysts can act as a singular light harvesting device that substantially enhances photocatalysis of important reactions.

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confidence: 80%

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation

et al. 2021

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“…However, it can be experimentally challenging and time-consuming to reveal underlying mechanisms and explore the vast material space of potential compounds, for which theoretical and computational methods could come to the rescue. They have a proven track record in modeling plasmonic hot-carrier generation − and transfer − and designing bimetallic compounds …”

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confidence: 99%

Single-Atom Dopants in Plasmonic Nanocatalysts

2023

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Bimetallic nanostructures combining plasmonic and catalytic metals are promising for tailoring and enhancing plasmonic hot-carrier generation utilized in plasmonic catalysis. In this work, we study the plasmonic hot-carrier generation in noble metal nanoparticles (Ag, Au, and Cu) with single-atom dopants (Ag, Au, Cu, Pd, and Pt) with first-principles time-dependent density functional theory calculations. Our results show that the local hot-carrier generation at the dopant atom is greatly altered by the dopant element while the plasmonic response of the nanoparticle as a whole is not significantly affected. In particular, hot holes at the dopant atom originate from the discrete d-electron states of the dopant, and the energies of these d-electron states and hence those of the hot holes depend on the dopant element, which opens up the possibility to tune hot-carrier generation with suitable dopants.

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“…If an electric field is applied to gold or silver nanoparticles with a frequency corresponding to a plasmonic resonance frequency of the system, the valence electrons of the nanoparticles will be excited and will slosh back and forth collectively. − This phenomenon is called localized surface plasmon resonance (LSPR), and LSPRs of gold and silver nanoparticles can be utilized in many areas such as photocatalysis, energy conversion, and biological sensing. − In the field of photocatalysis, plasmonic systems can be designed as catalysts to enhance chemical reactions such as water splitting, CO 2 reduction, H 2 dissociation, and N 2 dissociation. − A diverse set of plasmonic systems have been designed to accelerate the rate of the plasmon-driven reactions, and active sites on the plasmonic systems have been examined to improve the efficiency of the catalytic reaction. − According to current understanding, the LSPR process includes many sub-steps such as hot-carrier generation, hot-carrier relaxation, and thermalization, which cross over a wide range of timescales. − Due to the complexity of the plasmon-enhanced photocatalytic process, the mechanism behind this process is not yet fully understood. However, it is of interest to understand this mechanism so that the efficiency of the process can be improved.…”

Section: Introductionmentioning

confidence: 99%

Connectivity between Static Field and Continuous Wave Field Effects on Excitation-Induced H₂ Activation

Wang,

Aikens

2023

J. Phys. Chem. C

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Due to the tremendous applications of the plasmon resonance excitation process, such as improvements in catalytic efficiency due to plasmonic enhancement and/or hot-electron processes, understanding the mechanism behind these processes has become a popular topic in recent years. In this work, we focus on unraveling the mechanism of excitation-induced H2 activation using a simplified triangular Au6/Ag6 cluster to investigate the effects of the electric field on electron redistribution and bond activation. We applied both static and continuous wave fields to investigate how these fields affect the systems. Geometrical changes (such as bond lengthening), molecular orbital reordering (affecting the relative energies of orbitals corresponding to hot-electron and charge-transfer excited states), and electronic charge redistribution between the cluster and the adsorbate occur upon application of a static electric field. To study H2 activation, we apply Ehrenfest dynamics with real-time time-dependent density functional theory and examine how different excitation frequencies and polarizations affect bond activation. Moreover, electron-only dynamics are examined with real-time time-dependent density functional theory, and the time-dependent variations in the orbital populations and electronic transitions provide information about the excitation and relaxation processes of hot electrons with applied electric fields. The static field results represent structures that can be accessed during the evolution of the systems when applying continuous wave fields. Through these studies, the effects of static and continuous wave field effects on plasmon-induced H2 activation can be understood.

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Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters

Abstract: Light-driven plasmonic enhancement of chemical reactions on metal catalysts is a promising strategy to achieve highly selective and efficient chemical transformations. The study of plasmonic catalyst materials has traditionally focused...

Cited by 13 publications

References 89 publications

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation

Single-Atom Dopants in Plasmonic Nanocatalysts

Connectivity between Static Field and Continuous Wave Field Effects on Excitation-Induced H₂ Activation

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Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters

Abstract: Light-driven plasmonic enhancement of chemical reactions on metal catalysts is a promising strategy to achieve highly selective and efficient chemical transformations. The study of plasmonic catalyst materials has traditionally focused...

Cited by 13 publications

References 89 publications

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation

Single-Atom Dopants in Plasmonic Nanocatalysts

Connectivity between Static Field and Continuous Wave Field Effects on Excitation-Induced H2 Activation

Contact Info

Product

Resources

About

Connectivity between Static Field and Continuous Wave Field Effects on Excitation-Induced H₂ Activation