Effect of the structure and charge of Au10 clusters on adsorption of hydrocarbons

Пичугина, Д. А.; Lanin, S. N.; Kovaleva, N. V.; Lanina, K. S.; Shestakov, Alexander F.; Кузьменко, Н.Е.

doi:10.1007/s11172-010-0352-4

Cited by 15 publications

(21 citation statements)

References 18 publications

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“…Ethane was found to physisorb on an Au(111) surface with a binding energy of 0.25 eV [66], which is in agreement with the theoretical value of 0.22 eV [67]. A similarly weak binding has also been reported for ethane adsorption on small neutral clusters Au x (x = 3-5,10,20) ranging between 0.08 and 0.33 eV [68,69]. The interaction can be considerably enhanced by exchanging one Au atom by a Ni atom [69] or by positively charging the cluster [68].…”

Section: Introductionsupporting

confidence: 86%

“…A similarly weak binding has also been reported for ethane adsorption on small neutral clusters Au x (x = 3-5,10,20) ranging between 0.08 and 0.33 eV [68,69]. The interaction can be considerably enhanced by exchanging one Au atom by a Ni atom [69] or by positively charging the cluster [68]. Dehydrogenation has not been reported and is rather unlikely due to the low binding energy.…”

Section: Introductionmentioning

confidence: 56%

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Selective C H bond activation of ethane by free gold clusters

Lang

Bernhardt

Bakker

et al. 2019

International Journal of Mass Spectrometry

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The activation and potential dissociation of ethane mediated by small cationic gold clusters Au x + (x = 2-4) has been explored by infrared multiphoton dissociation (IR-MPD) spectroscopy and density functional theory (DFT) calculations. The calculations show that the interaction between the gold clusters and ethane is mainly governed by the mixing of the ethane CH 3 bond-forming orbitals-(CH 3) with gold d-orbitals. While the CC single bond appears to be unaffected, this mixing leads to the selective activation of up to two ethane C-H bonds and a reduction of the activation barrier for C-H bond dissociation to up to 0.82 eV, making the reaction kinetically feasible at room temperature. In agreement with this, experimental IR-MPD spectra of the complexes Au 2 (C 2 H 6) 2 + and Au 2 (C 2 D 6) 2 + reveal that the dominant product is one where a single ethane C-H bond is dissociated resulting in a complex which contains an ethyl group and a bridge-bonded H atom along with a second, adsorbed C 2 H 6 molecule. A similar C-H bond dissociation mechanism is theoretically predicted for the Au 3 (C 2 H 6) y + (y = 2,3) and Au 4 (C 2 H 6) y + (y = 2,3) complexes, albeit thermodynamically less favorable. IR-MPD spectra of Au 3 (C 2 H 6) y + (y = 2,3) and Au 4 (C 2 H 6) y + (y = 2,3) confirm the encounter product to be the dominant one, although the coexistence of isomers containing ethyl groups cannot be excluded. Various pathways for C-H bond activation are theoretically explored and the ethane activation mechanism is compared to the gold mediated activation of methane and ethylene. 65 spectra (I 0) in between successive FELICE pulses. The IR-MPD spectra shown in this contribution display the ratio 65

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Section: Introductionsupporting

confidence: 86%

Section: Introductionmentioning

confidence: 56%

Selective C H bond activation of ethane by free gold clusters

Lang

Bernhardt

Bakker

et al. 2019

International Journal of Mass Spectrometry

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“…For over a decade, free clusters have been shown to represent suitable and versatile model systems to mimic the catalytically active sites of heterogeneous catalysts [26][27][28][29][30]. These studies revealed that small neutral and anionic gold clusters preferably bind ethylene in a -like configuration with the exception of the neutral Au atom and the Au 5 cluster [31][32][33][34][35]. The only systematic study on cationic clusters (Au x + , x = 1-10) was reported by Lyalin and Taketsugu showing the preferred adsorption of one C 2 H 4 molecule in a -bonded configuration [31].…”

Section: Introductionmentioning

confidence: 99%

The interaction of ethylene with free gold cluster cations: infrared photodissociation spectroscopy combined with electronic and vibrational structure calculations

Lang

Bernhardt

Bakker

et al. 2018

J. Phys.: Condens. Matter

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The interaction of ethylene with free gold clusters of different sizes and charge states has been previously shown theoretically to involve two different adsorption modes of the C 2 H 4 molecule, namely: the di-and-bonded ethylene adsorption configurations. Here, we present the first experimental investigation of the structure of a series of gas-phase gold-ethylene complexes, Au x (C 2 H 4) y + (x =2-4, y =1-3). By employing infrared multiple-photon dissociation spectroscopy (IR-MPD) in conjunction with first-principles calculations it is uncovered that up to three C 2 H 4 molecules bind to gold cations exclusively in a-bonded configuration. The binding of all ethylene molecules is found to be dominated by partial electron donation from the ethylene molecules to the gold clusters leading to an activation of the CC bond. The cooperative action of multiple coadsorbed C 2 H 4 on Au 4 + is shown to enable additional charge back-donation and an enhanced CC bond activation. In contrast, the strong C-H bond is not weakened and the experimental spectra do not give any indication for C-H bond dissociation. The possible correlations of the CC bond stretch vibration with the CC bond length and the net charge transfer are discussed.

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“…33 The catalytic activity of Au/FeO x in CO oxidation is just due to the presence of Au 10 clusters on the surface. Recently, 146,147 we used the Au 10 cluster with the bilayer structure as model in the quantum chemical studies of the adsorption and catalytic properties of gold clusters. The catalytic activity of atomic gold clusters Au n (n = 2, 6 ± 9, 12, 18, 20) supported on MgO in CO oxidation was studied.…”

Section: Methodsmentioning

confidence: 99%

“…The activity of such cationic sites in activation of unsaturated hydrocarbons was predicted theoretically for ligand-free gold clusters. 144,146 Establishment of the mechanism of catalytic selective oxidation of styrene in the presence of gold clusters with certainty requires an additional theoretical research.…”

Section: Viii2 Application Of Au N (Sr) M and Au N (Pr 3 ) M Clustementioning

confidence: 99%