Activation of Molecular Oxygen by Anionic Gold Clusters

Woodham, Alex P.; Meijer, Gerard; Fielicke, André

doi:10.1002/anie.201108958

Cited by 106 publications

(112 citation statements)

References 39 publications

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“…66 Recently, the 4Y_O 2 (side) structure was suggested from the study of the O−O stretching frequencies of Au n O 2 − by Fielicke and co-workers. 12 The O 2 −BEs of the 4Y_O 2 (side) and 4Y_O 2 (apex) are 1.09/1.01 and −0.07/0.41 eV at the MP2/BPW91 level, respectively. The 4Y_O 2 (side) is more stable than the 4Y_O 2 (apex) structure.…”

Section: Computational Methods and Issuesmentioning

confidence: 97%

Geometrical and Electronic Characteristics of Au_nO₂^– (n = 2–7)

Lee

et al. 2015

J. Phys. Chem. C

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Most density functionals do not properly describe the characteristics of superoxide (O 2 − ) (i.e., first two vertical electron detachment energies and the excitation energies of neutralized singlet state) of small even-numbered Au n O 2 − clusters. However, the second-order Møller−Plesset theory (MP2) shows significant charge transfer from Au cluster anions to oxygen molecule and so provides proper electronic characteristics of superoxide of small even-numbered Au n O 2 − clusters. This has allowed us to properly describe the properties of even-numbered Au n O 2 − clusters. Even in the case of odd-numbered Au n O 2 − clusters, we find that Au 5 − is a chemically O 2 -adsorbed singlet state at 0 K, against a commonly accepted physisorbed triplet state. This is further evidenced by our extensive coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] calculations, including the relativistic effect. However, the entropy effect makes the physisorbed triplet state more stable than the chemisorbed singlet state at higher temperatures, consistent with the experiment. The weak O 2 binding by odd-numbered cluster anions (n = 3, 5, and 7) could be further weakened by the entropic effect, which results in van der Waals complexes at high temperatures. The present study reports the geometrical and electronic characteristics of small Au n O 2 − (n = 2−7) clusters including isomers, which match the corresponding photoelectron spectra (PES).

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Section: Computational Methods and Issuesmentioning

confidence: 97%

Geometrical and Electronic Characteristics of Au_nO₂^– (n = 2–7)

Lee

et al. 2015

J. Phys. Chem. C

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“…[31][32][33] Several possible routes for O 2 activation have been proposed, including direct or adsorbate-assisted dissociation, [34][35][36][37][38] the formation of superoxo (O 2 -) or peroxo (O 2 2-) complexes, [39][40][41][42][43] and activation via a hydroperoxyl (OOH) intermediate. [44][45][46][47][48] Recently, we revealed that even on bulk Au(111) surface molecular O 2 can be activated via * OOH radical produced by abstracting a H atom from co-adsorbed methanol or water.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Studies on the Synergetic Effects of Au–Pd Bimetallic Catalysts in the Selective Oxidation of Methanol

et al. 2015

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The selective oxidation of methanol to formaldehyde with molecular O 2 on Au-Pd alloy surfaces has been studied by using density functional theory (DFT). We show that the existence of Pd remarkably improves the adsorption and activation of O 2 on Au-Pd surfaces. In particular, the second-neighbor Pd monomer pair (Pd-SNMP) surrounded by gold atoms can provide unique active sites for the co-adsorption of O 2 …CH 3 OH, thus facilitating the activation of O 2 via a hydroperoxyl radical ( * OOH). With the involvement of * OOH and its decomposed fragments ( * O and * OH), the oxidative dehydrogenation of methanol to formaldehyde is facilely achieved on bimetallic Au-Pd surfaces, the barriers of which are calculated to be 0.02-0.45 eV on Au 2 Pd/(111) and AuPd/(100) surfaces.Importantly, we find that the unusual activation of O 2 via an OOH-pathway instead of direct dissociation on Au-Pd catalysts is mainly responsible for the enhanced activity and selectivity in the selective oxidation of alcohols. This hydroperoxyl-based mechanism reveals the intrinsic synergy of Au-Pd bimetallic catalysts in the selective oxidation of alcohols and may provide insights for designing better bimetallic catalysts.

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“…They found a strong dependence of reactivity on both cluster size (n) and charge state (q); for Au n − , only even-numbered (even-n) clusters reacted with oxygen. Salisbury et al 4 described a series of experiments on the adsorption of O 2 on gold cluster anions Au n − with n = 2− 22; they showed that only certain clusters (n = 2, 4, 6,8,10,12,14,18,20) exhibit measurable adsorption, and no reaction was detected for any odd-numbered cluster, nor for n = 16. A more detailed experimental study of O 2 on Au n − with n = 1−7 was performed by Huang et al, 8 who provided further insight into O 2 interactions with small gold clusters.…”

Section: Introductionmentioning

confidence: 99%

“…Calculated (Vertical) Ionization Potential (IP, eV) for the M n Clusters a The calculated IPs are given for two closely lying isomers for M 3 , M 4 , and M 10 and three for Au10 . b Reference 50. c Reference 51.…”

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confidence: 99%

Theoretical Comparative Study of Oxygen Adsorption on Neutral and Anionic Ag_n and Au_n Clusters (n = 2–25)

2014

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Using density functional theory, we performed a theoretical comparative study of oxygen adsorption on neutral and anionic Ag n and Au n clusters in a large size range of n = 2−25. Ionization potentials (IPs) and electron affinities (EAs) of the pure clusters and the M n q −O 2 binding energies E bind (M n q −O 2 ) in the (M n O 2 ) q complexes (M = Ag, Au; q = 0, −1) were determined. Three density functionals, namely, BP86, revPBE, and B3LYP, were used in the calculations, among which the BP86 functional gave the best results for IPs and EAs, while B3LYP gave the best results for E bind (M n q −O 2 ). A number of differences between the silver and gold clusters and their reactivities toward O 2 adsorption are accounted for by the calculations. One interesting result is that the calculated Au n − −O 2 binding energies are in good, quantitative agreement with the measured relative reactivities of the Au n − cluster anions toward O 2 adsorption.

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Activation of Molecular Oxygen by Anionic Gold Clusters

Cited by 106 publications

References 39 publications

Geometrical and Electronic Characteristics of Au_nO₂^– (n = 2–7)

Geometrical and Electronic Characteristics of Au_nO₂^– (n = 2–7)

Theoretical Studies on the Synergetic Effects of Au–Pd Bimetallic Catalysts in the Selective Oxidation of Methanol

Theoretical Comparative Study of Oxygen Adsorption on Neutral and Anionic Ag_n and Au_n Clusters (n = 2–25)

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Activation of Molecular Oxygen by Anionic Gold Clusters

Cited by 106 publications

References 39 publications

Geometrical and Electronic Characteristics of AunO2– (n = 2–7)

Geometrical and Electronic Characteristics of AunO2– (n = 2–7)

Theoretical Studies on the Synergetic Effects of Au–Pd Bimetallic Catalysts in the Selective Oxidation of Methanol

Theoretical Comparative Study of Oxygen Adsorption on Neutral and Anionic Agn and Aun Clusters (n = 2–25)

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Geometrical and Electronic Characteristics of Au_nO₂^– (n = 2–7)

Geometrical and Electronic Characteristics of Au_nO₂^– (n = 2–7)

Theoretical Comparative Study of Oxygen Adsorption on Neutral and Anionic Ag_n and Au_n Clusters (n = 2–25)