Prediction of a low-temperature N
            <sub>2</sub>
            dissociation catalyst exploiting near-IR–to–visible light nanoplasmonics

Martirez, John Mark P.; Carter, Emily A.

doi:10.1126/sciadv.aao4710

Cited by 88 publications

(109 citation statements)

References 72 publications

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“…For silver and gold clusters the electrostatic potential surface shows similar features as copper clusters, suggesting that such coinage metal clusters have suitable sizes for enhanced catalytic activity. These results on small clusters are consistent with the recent prediction of the efficient catalytic activity of a Mo doped Au(111)‐gold‐surface, leading to a promising low‐temperature N 2 dissociation toward NH 3 production which can have a deep impact in a new generation in the Born‐Haber process …”

Section: Resultssupporting

confidence: 90%

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

Gam

Arratia‐Pérez

Kahlal

et al. 2019

Int J of Quantum Chemistry

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Density functional theory (DFT) calculations were carried out on a series of clusters made of a centered tetrahedral 16‐atom superatomic cage having 20 or 18 jellium electrons (je) and structurally related to [Au20], namely [X@M16] (M = group 11; X = group 2, 4, 12, 14 element). Such species provide further information of how two different electron counts offer a more preferred endohedral situation for specific group elements. Calculations show that the encapsulated atom provides supplementary orbitals to stabilize the bonding M16 MO's. Different favored electron counts are found depending on the nature of the encapsulated atom, as observed by the formation of 20‐je species when encapsulating a group 14 element and 18‐je species when encapsulating a group 2 element. In addition, the capabilities to enable reactive sites along the cage structure are found via the formation of σ holes at the coinage‐metal edges, as shown by their electrostatic potential surface. Such naked species, which constitute an interesting addition to libraries of examples as small models for doped M(111) surfaces of fcc metals, reveal that different superatomic electronic configurations can favor the encapsulation of certain group elements. These results can guide further design of endohedral species.

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Section: Resultssupporting

confidence: 90%

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

Gam

Arratia‐Pérez

Kahlal

et al. 2019

Int J of Quantum Chemistry

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“…In sharp contrast, the T d ‐[W@Au 12 Pt 4 ] exhibits regions with smaller value of V s ( r ), leading a very site‐specific region expected for catalytic activity located at the center of each Au(111)‐like face, where each Pt atom is allocated. This situation is comparable to the recent prediction of the efficient catalytic activity of a Mo doped Au(111)‐gold‐surface, leading to a promising low‐temperature N 2 dissociation toward NH 3 production which can have a deep impact in a new generation in the Born‐Haber Process . Thus, T d ‐W@Au 12 Pt 4 can be a useful model to explore the catalytic activity of different clusters retaining a high gold/dopant ratio.…”

Section: Resultssupporting

confidence: 82%

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au₁₂Pt_n (n = 0‐4) superatomic clusters from relativistic DFT calculations

Gam

Arratia‐Pérez

Kahlal

et al. 2018

Int J of Quantum Chemistry

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Attempts to expand the versatility of well defined clusters are a relevant issue in the design of building blocks for functional nanostructures. Here, we investigate the plausible formation of related structures from the emblematic highly symmetrical 18‐e [W@Au12] cluster. The calculated [W@Au12Ptn] series, with n = 0, 1, 2, 3, and 4, show cohesion energies, HOMO‐LUMO gap, adiabatic electron affinities (AEAs) and adiabatic ionization potentials (AIPs), indicating a relative stability to the parent cluster [W@Au12] experimentally characterized, where clusters with n = 1 and n = 4 are suggested as the most stable with respect to oxidation. The resulting symmetry lowering away from the high icosahedral symmetry upon adding Pt atoms induces a sizable splitting of the frontiers shells, which in turn effectively modify the properties of the calculated clusters, as observed from calculated optical properties. The estimated absorption spectra show an interesting broadening effect of the absorption peaks, which appears as a useful approach for further design of broad black absorbers, which are able to absorb light in a wider range, with potential capabilities to enhance the efficiency of thin film solar cells and photocatalysis processes, among other applications.

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“…74 For this reason, the real opportunities for non-thermal mediated reactions -where the excited state of the system needs to be accessed -are still mostly unknown. 23,74,75 As such, it might be possible that new materialsnot considered catalytic up to now for the ground PES of a chemical reaction -may present an interesting excited state energy landscape for the adsorbed molecules The combination of these excited-state photocatalytic materials with plasmonic NPs may open new routes for the field. Indeed, plasmonic hybrid nanostructures are an appealing route for combining material properties to enhance chemical reactivity.…”

Section: Outlook and Perspectivesmentioning

confidence: 99%

From Optical to Chemical Hot Spots in Plasmonics

et al. 2019

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In recent years, the possibility to induce chemical transformations by using tunable plasmonic modes has opened the question of whether we can control or create chemical hot spots in these systems. This can be rationalized as the reactive analogue of the well-established concept of optical hot spots, which have drawn a great deal of attention to plasmonic nanostructures for their ability to circumvent the far-field diffraction limit of conventional optical elements. The parameters that determine the reactivity of plasmonic systems are deeply influenced by the dynamics and interplay of photons, plasmon-polaritons, carriers, phonons and molecular states. Although optical hot spots can be mainly defined by the geometry and permittivity of the nanostructures, the degrees of freedom influencing their photocatalytic properties appear to be much more numerous. These degrees of freedom can affect the reaction rates, the product selectivity or the spatial localization of a chemical reaction. In this Account, we show how the control of chemical hot spots can be achieved by carefully tuning the parameters that influence the cascade of events following the optical excitation of plasmonic modes in nanostructures. We discuss here a series of single photocatalyst techniques and ideas of how plasmonic nanoscale reactivity can be spatially mapped and imaged, and how the lifetime of hot and thermalized carriers can be altered by trap states on semiconductors and by metal-semiconductor interfaces. In addition, the tailored generation of non-thermal phonons in metallic nanostructures and their dissipation is shown as a promise to understand and exploit thermal photocatalysis at the nanoscale. Surpassing or enhancing each of these energy channels should enable to engineer solar nanometric photocatalysts. Nevertheless, the ultimate capability of a plasmonic photocatalyst to trigger a chemical reaction is correlated to its ability to navigate through, or even modify, the potential energy surface of a given chemical reaction. Here we reunite both worlds, the plasmonic photocatalysts and the molecular ones, identifying different energy transfer pathways and their influence on selectivity and efficiency of chemical reactions. We foresee that the migration from optical to chemical hot spots will greatly assist the understanding of ongoing plasmonic chemistry.

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Prediction of a low-temperature N ₂ dissociation catalyst exploiting near-IR–to–visible light nanoplasmonics

Abstract: We propose a promising new method of solar-driven ammonia synthesis with metal nanoparticles.

Cited by 88 publications

References 72 publications

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au₁₂Pt_n (n = 0‐4) superatomic clusters from relativistic DFT calculations

From Optical to Chemical Hot Spots in Plasmonics

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Prediction of a low-temperature N 2 dissociation catalyst exploiting near-IR–to–visible light nanoplasmonics

Abstract: We propose a promising new method of solar-driven ammonia synthesis with metal nanoparticles.

Cited by 88 publications

References 72 publications

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

Stabilizing heteroatom‐centered 16‐vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au12Ptn (n = 0‐4) superatomic clusters from relativistic DFT calculations

From Optical to Chemical Hot Spots in Plasmonics

Contact Info

Product

Resources

About

Prediction of a low-temperature N ₂ dissociation catalyst exploiting near-IR–to–visible light nanoplasmonics

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au₁₂Pt_n (n = 0‐4) superatomic clusters from relativistic DFT calculations