Study of odd–even effects in physisorption and chemisorption of Ar, N2, O2and NO on open shell Ag11–13+clusters by means of self-consistent van der Waals density functional calculations

Fernández, Eva M.; Balbás, L. C.

doi:10.1039/c9cp04865k

Cited by 4 publications

(4 citation statements)

References 64 publications

(130 reference statements)

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“…We compare the binding energy differences of CO and O 2 on pure Ag n + clusters and CO on Ag n O + clusters in Figure . We found that the closed-shell Ag 7 + and Ag 9 + clusters have low reactivity toward O 2 , in good agreement with a previous study . Meanwhile, all Ag n + clusters are reactive to CO, which are different from the negatively charged Ag n – clusters that were reported as inert toward CO .…”

Section: Resultssupporting

confidence: 91%

“…clusters have low reactivity toward O 2 , in good agreement with a previous study. 46 Meanwhile, all Ag n + clusters are reactive to CO, which are different from the negatively charged Ag n − clusters that were reported as inert toward CO. 47 However, the low activity of closed-shell Ag n + clusters toward O 2 makes them unsuitable for CO oxidation. Therefore, it is necessary to add atomic O species in Ag n + clusters to provide new active sites and even alter the reaction mechanism.…”

Section: Calculation Of Co Oxidation On Agmentioning

confidence: 91%

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Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag₁₅O⁺ with Remarkable Stability

Xing

et al. 2021

J. Phys. Chem. C

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Silver-based materials are reported to have remarkable catalytic activity toward CO oxidation after O2 pretreatment, which are less expensive in comparison with conventional catalysts such as gold and platinum. However, the regulatory role of atomic O that is inevitably present on silver surface remains unclear due to the complicated circumstances in condensed phases. Here we investigated CO oxidation on silver clusters doped by a single O atom Ag n O+ (n = 7–11, 15, 19, 22) by experimental mass spectrometry combined with ab initio calculations. We found two types of O species having high cluster size selectivity and determining the oxidation products. A higher d-band center of Ag n O+ leads to larger reaction barrier. Remarkably, an extremely stable Ag15O+ superatom with a unique meteor dart structure and satisfying the 18 valence electrons configuration (1S21P61D102S0) was discovered, which is the first reported O-doped transition metal cluster with superatomic character. This work provides important knowledge for balancing the stability and activity of silver-based catalysts at atomic precision for oxidation reactions.

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Section: Resultssupporting

confidence: 91%

Section: Calculation Of Co Oxidation On Agmentioning

confidence: 91%

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag₁₅O⁺ with Remarkable Stability

Xing

et al. 2021

J. Phys. Chem. C

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“…As advised in the bibliography concerning the adsorption of small molecules on Ag n clusters, − a dispersion-corrected functional was used, i.e. , the optB86b-vdW functional .…”

Section: Computational Detailsmentioning

confidence: 99%

Coordination of Ethylamine on Small Silver Clusters: Structural and Topological (ELF, QTAIM) Analyses

et al. 2022

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Amine ligands are expected to drive the organization of metallic centers as well as the chemical reactivity of silver clusters early growing during the very first steps of the synthesis of silver nanoparticles via an organometallic route. Density functional theory (DFT) computational studies have been performed to characterize the structure, the atomic charge distribution, and the planar two-dimensional (2D)/three-dimensional (3D) relative stability of small-size silver clusters (Ag n , 2 ≤ n ≤ 7), with or without an ethylamine (EA) ligand coordinated to the Ag clusters. The transition from 2D to 3D structures is shifted from n = 7 to 6 in the presence of one EA coordinating ligand, and it is explained from the analysis of the Ag–N and Ag–Ag bond energies. For fully EA saturated silver clusters (Ag n –EA n ), the effect on the 2D/3D transition is even more pronounced with a shift between n = 4 and 5. Subsequent electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM) topological analyses allow for the fine characterization of the dative Ag–N and metallic Ag–Ag bonds, both in nature and in strength. Electron transfer from ethylamine to the coordinated silver atoms induces an increase of the polarization of the metallic core.

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“…Silver clusters are ideal model systems to study the active sites of silver-based catalysts and several theoretical concepts, and have been intensively studied. [7][8][9][10][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] The mass spectrometry experiments revealed an odd-even oscillation of the abundances of Ag n + , in which the odd sizes with an even number of valence electrons are more abundant than their neighbors. 39 In addition to the odd-even oscillation trend, the ion intensities decrease sharply after the sizes of n = 3, 9, and .…”

Section: Introductionmentioning

confidence: 99%

The global minimum of Ag₃₀: a prolate spheroidal structure predicted using a genetic algorithm with incomplete local optimizations at the DFT level

Hang

et al. 2023

Phys. Chem. Chem. Phys.

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Study of odd–even effects in physisorption and chemisorption of Ar, N₂, O₂and NO on open shell Ag_11–13⁺clusters by means of self-consistent van der Waals density functional calculations

Abstract: Electronic and structural odd-even effects in the adsorption of small molecules on open shell silver cationic clusters have been rationalized.

Cited by 4 publications

References 64 publications

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag₁₅O⁺ with Remarkable Stability

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag₁₅O⁺ with Remarkable Stability

Coordination of Ethylamine on Small Silver Clusters: Structural and Topological (ELF, QTAIM) Analyses

The global minimum of Ag₃₀: a prolate spheroidal structure predicted using a genetic algorithm with incomplete local optimizations at the DFT level

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Study of odd–even effects in physisorption and chemisorption of Ar, N2, O2and NO on open shell Ag11–13+clusters by means of self-consistent van der Waals density functional calculations

Abstract: Electronic and structural odd-even effects in the adsorption of small molecules on open shell silver cationic clusters have been rationalized.

Cited by 4 publications

References 64 publications

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag15O+ with Remarkable Stability

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag15O+ with Remarkable Stability

Coordination of Ethylamine on Small Silver Clusters: Structural and Topological (ELF, QTAIM) Analyses

The global minimum of Ag30: a prolate spheroidal structure predicted using a genetic algorithm with incomplete local optimizations at the DFT level

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Study of odd–even effects in physisorption and chemisorption of Ar, N₂, O₂and NO on open shell Ag_11–13⁺clusters by means of self-consistent van der Waals density functional calculations

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag₁₅O⁺ with Remarkable Stability

Single O Atom Doped Ag Cluster Cations for CO Oxidation: An O-Doped Superatom Ag₁₅O⁺ with Remarkable Stability

The global minimum of Ag₃₀: a prolate spheroidal structure predicted using a genetic algorithm with incomplete local optimizations at the DFT level