Correlation between electronic properties and reactivity toward oxygen of tetrahedral gold–silver clusters

Polynskaya, Yulia G.; Пичугина, Д. А.; Кузьменко, Н.Е.

doi:10.1016/j.comptc.2014.12.025

Cited by 14 publications

(12 citation statements)

References 78 publications

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“…Additionally, the reaction is almost thermoneutral. Furthermore, O 2 dissociation was also proposed to be endothermic for the neutral pyramidal Au 20 cluster …”

Section: Effect Of the Surface Geometry On O2 Dissociationmentioning

confidence: 98%

“…Adsorption of O 2 onto small, unsupported Au n q (with n = 1–55 and q = −1,0,1) clusters has been extensively studied using DFT. ,,− Although the adsorption strength as well as the geometry depend on the calculation details, such as the employed exchange-correlation functional, several trends can be extracted.…”

Section: Effect Of the Surface Geometry On O2 Dissociationmentioning

confidence: 99%

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O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

et al. 2017

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The activation of O on metal surfaces is a critical process for heterogeneous catalysis and materials oxidation. Fundamental studies of well-defined metal surfaces using a variety of techniques have given crucial insight into the mechanisms, energetics, and dynamics of O adsorption and dissociation. Here, trends in the activation of O on transition metal surfaces are discussed, and various O adsorption states are described in terms of both electronic structure and geometry. The mechanism and dynamics of O dissociation are also reviewed, including the importance of the spin transition. The reactivity of O and O toward reactant molecules is also briefly discussed in the context of catalysis. The reactivity of a surface toward O generally correlates with the adsorption strength of O, the tendency to oxidize, and the heat of formation of the oxide. Periodic trends can be rationalized in terms of attractive and repulsive interactions with the d-band, such that inert metals tend to feature a full d band that is low energy and has a large spatial overlap with adsorbate states. More open surfaces or undercoordinated defect sites can be much more reactive than close-packed surfaces. Reactions between O and other species tend to be more prevalent than reactions between O and other species, particularly on more reactive surfaces.

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“…Additionally, the reaction is almost thermoneutral. Furthermore, O 2 dissociation was also proposed to be endothermic for the neutral pyramidal Au 20 cluster …”

Section: Effect Of the Surface Geometry On O2 Dissociationmentioning

confidence: 98%

Section: Effect Of the Surface Geometry On O2 Dissociationmentioning

confidence: 99%

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

et al. 2017

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“…Au 19 Li, Au 19 Cu, Au 19 Ag, and Au 19 Pt are found to retain the pyramidal geometry of Au 20 46 – 51 . Increasing the Ag concentration induces the energy gap and optical transition of Au 19− n Ag n 48 , 49 . Au 19 Cu and Au 19 Pd clusters are potential for adsorption of trivalent arsenic 50 .…”

Section: Introductionmentioning

confidence: 99%

Au19M (M=Cr, Mn, and Fe) as magnetic copies of the golden pyramid

Tam

Cuong

Pham

et al. 2017

Sci Rep

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An investigation on structure, stability, and magnetic properties of singly doped Au19M (M=Cr, Mn, and Fe) clusters is carried out by means of density functional theory calculations. The studied clusters prefer forming magnetic versions of the unique tetrahedral Au20. Stable sextet Au19Cr is identified as the least reactive species and can be qualified as a magnetic superatom. Analysis on cluster electronic structures shows that the competition between localized and delocalized electronic states governs the stability and magnetic properties of Au19M clusters.

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“…However, intermediate electron counts are interesting cases that expand the libraries and versatility of superatomic clusters, denoting two‐dimensional magic numbers of valence electrons (ie, 6, etc.) as discussed earlier by Janssens et al The incorporation of dopant elements has been demonstrated to be an interesting approach to modulate cluster properties, allowing us to explore and understand further stability and bonding situations …”

Section: Introductionmentioning

confidence: 91%

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

Quintana

Ocayo

Guajardo‐Maturana

et al. 2019

Int J of Quantum Chemistry

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Superatomic clusters offer useful templates displaying distinctive physical and chemical characteristics. Here, we explore the [M@Au 8 (PPh 3 ) 8 ] n+ (M = Au, n = 3; Pd, Pt, n = 2) robust framework to gain an understanding of the nature of the inclusion of mercury atoms at Au 4 faces, leading to [M@Au 8 Hg x (PPh 3 ) 8 ] n+ (x = 1, 2). Our results show a weak interaction of about 25 kcal mol −1 per Hg atom, which is mainly of electrostatic character, followed by orbital and London dispersion-type interactions. This weak interaction can be understood as the formation of host-guest species, for which the inherent electronic and optical properties of the [M@Au 8 (PPh 3 ) 8 ] cluster along the series do not vary to a large extent. This demonstrates that, in [M@Au 8 Hg x (PPh 3 ) 8 ], each Hg can be considered an inclusion atom rather than a dopant element, where the parent cluster is able to act as a Lewis acid host. Furthermore, the viable formation of such species can serve as useful examples to stimulate future experimental characterization of inclusion complexes involving related superatomic structures with available open faces. K E Y W O R D S clusters, gold clusters, Lewis-acid, mercury

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Correlation between electronic properties and reactivity toward oxygen of tetrahedral gold–silver clusters

Cited by 14 publications

References 78 publications

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Au19M (M=Cr, Mn, and Fe) as magnetic copies of the golden pyramid

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

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Correlation between electronic properties and reactivity toward oxygen of tetrahedral gold–silver clusters

Cited by 14 publications

References 78 publications

O2Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

O2Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Au19M (M=Cr, Mn, and Fe) as magnetic copies of the golden pyramid

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au8Hgx(PPh3)8]n+ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations

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Product

Resources

About

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

O₂Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Nature of mercury inclusion in intermediate 6‐valence electron [M@Au₈Hg_x(PPh₃)₈]ⁿ⁺ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations