Size-dependent reactivity of cobalt cluster ions with nitrogen monoxide: Competition between chemisorption and decomposition of NO

Hanmura, Tetsu; Ichihashi, Masahiko; Okawa, Ryuji; Kondow, Tamotsu

doi:10.1016/j.ijms.2008.08.024

Cited by 16 publications

(34 citation statements)

References 26 publications

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“…This reaction was also observed with or without release of metal atoms for other bare metal and metal oxide clusters such as Co n + , 38,39 Cu n O 2 − , 24 Nb n + , 40 and Rh n ± . 41,42 The NO adsorption probability, the selective activity toward NO [σ r (NO)/σ r (O 2 )], and the NO decomposition efficiency of Cu n Al + are roughly compared with those of Co n + and Cu n O 2 − , which can be obtained mainly from our previous data.…”

Section: The Journal Of Physical Chemistry Amentioning

confidence: 60%

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Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O₂

Hirabayashi

Ichihashi

2015

J. Phys. Chem. A

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Aluminum-doped copper cluster cations, CunAl(+), were produced via an ion sputtering method and analyzed by mass spectrometry. The measured size distributions show that Cu6Al(+) and Cu18Al(+) are highly stable species, which can be understood in terms of the electronic subshell 1P and 2S closings, respectively. Furthermore, the reactions of size-selected CunAl(+) (n = 4-6 and 8-16) with NO and O2 were studied at near thermal energies by using a tandem-type mass spectrometer. The doping of an Al atom improves the reactivity of the clusters toward NO in particular for n = 9, 11, 13, and 15, whereas it does not change the reactivity toward O2 significantly. Consequently, it was found that CunAl(+) (n = 9, 11, 13 and 15) are more reactive toward NO than toward O2. The high reactivity of Cu9Al(+) toward NO compared to that of Cu10(+) is explained in terms of the increase of the adsorption energy and the lowering of the barrier to dissociative adsorption, with the aid of calculations based on density functional theory. Moreover, the multiple-collision reactions of CunAl(+) (n = 9, 11, and 13) with NO result in the production of cluster dioxides, Cun-3AlO2(+), (i.e., release of N2), which clearly indicates that NO decomposition proceeds on these clusters.

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Section: The Journal Of Physical Chemistry Amentioning

confidence: 60%

“…The Journal of Physical Chemistry A Article × 10 −4 Torr 38. This result indicates that NO decomposition proceeds less efficiently on Cu n Al + than Co n+1 + and Cu n−1 O 2 with the same number of atoms.…”

mentioning

confidence: 93%

Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O₂

Hirabayashi

Ichihashi

2015

J. Phys. Chem. A

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“…In fact, similar experiments were carried out for the reactions of Co n + + NO. 12 To examine the above reaction pathways, the structures and energies of the reactants, intermediates, and products in the reaction of Cu 8 O 2 − + 2NO → Cu 6 O 4 − + [2Cu, N 2 ] were calculated by the DFT method. For all species, the vibrational frequency analysis was performed in order to confirm that they have local minimum energies on the potential energy surface.…”

Section: Discussionmentioning

confidence: 99%

“…Similar metal atom release had been observed in the reactions of small Co n + clusters with NO, where NO decomposition proceeds under multiple collision conditions. 11,12 In this further study, we have focused on multiple collision reactions of Cu n O 2 − (n = 8, 10, and 12) with NO. The intensities of reaction product ions are measured by varying the NO gas pressure to find evidence of NO decomposition.…”

Section: Introductionmentioning

confidence: 99%

NO Decomposition Activated by Preadsorption of O₂ onto Copper Cluster Anions

Hirabayashi

Ichihashi

2015

J. Phys. Chem. C

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Reactions of anionic copper cluster dioxides, Cu n O 2 − (n = 8, 10, and 12), with NO were studied in the gas phase by using a guided ion beam tandem mass spectrometer. A product ion, Cu n−2 O 4 − , is observed under multiple collision conditions together with the single-collision reaction products, Cu n O 2 NO − and Cu n−1 O 2 NO − . The NO-pressure dependence studies show that Cu n−2 O 4 − is formed via adsorption of two NO molecules followed by releasing an N 2 molecule, which is clear evidence for NO decomposition. Density functional theory calculations were also performed for the reaction of Cu 8 O 2 − with two NO molecules and confirm the production of Cu 6 O 4 − under the experimental conditions used.

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“…_ 9 we can therefore conclude that the spin magnetic moment is determined by t he number of 3d holes and that the hole spin polarizat ion is 100 %. Applying these constraints we can assign the number of holes hd and the corresponding spin multiplicities and orbital magnetic moments for each cluster size as listed in Cot (cro s) , Hanmura09 [28] for Cot _ 7 (pentagons) , Gchrkc09 [23] for Cot -s (full circles) , Kiawi15 [24] for Cot, 9 (squares) , and Martinez13 [29] for Cot_ 9 (stars) are also shown. The lines are guides to the eye.…”

Section: Size Dependent Spin and Orbital Magnetic Momentsmentioning

confidence: 99%

Large orbital magnetic moments of small, free cobalt cluster ions Co${_n^+}$ with n ${ \leqslant 9}$

Zamudio-Bayer¹,

Hirsch²,

Langenberg³

et al. 2018

J. Phys.: Condens. Matter

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The size dependent electronic structure and separate spin and orbital magnetic moments of free eo;t (n = 4 9) cluster ions have been invest igated by x-ray ab orption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap.A very large orbital magnetic moment of 1.4 ± 0.1 /.LB per atom was determined for Cot , which is one order of magnitude larger than in the bulk metal. Large orbital magnetic moments per atom of~ 1 /.LB were also determined for CoJ , Cot , and Cot.The orbital contribution to the total magnetic moment shows a non-monotonic cluster sizo dependence: T he orbital contribution increases from a local minimum at n = 2 to a local maximum at n = 5 and then decreases with increasing cluster size. The 3d spin magnetic moment per atom is nearly constant and is solely defined by the number of 3d holes which shows t hat t he 3d majority ~pin st ates arc fully occupied , t hat is, 3d hole spin polarization is 100%.

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Size-dependent reactivity of cobalt cluster ions with nitrogen monoxide: Competition between chemisorption and decomposition of NO

Cited by 16 publications

References 26 publications

Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O₂

Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O₂

NO Decomposition Activated by Preadsorption of O₂ onto Copper Cluster Anions

Large orbital magnetic moments of small, free cobalt cluster ions Co${_n^+}$ with n ${ \leqslant 9}$

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Size-dependent reactivity of cobalt cluster ions with nitrogen monoxide: Competition between chemisorption and decomposition of NO

Cited by 16 publications

References 26 publications

Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O2

Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O2

NO Decomposition Activated by Preadsorption of O2 onto Copper Cluster Anions

Large orbital magnetic moments of small, free cobalt cluster ions Co${_n^+}$ with n ${ \leqslant 9}$

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Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O₂

Stability of Aluminum-Doped Copper Cluster Cations and Their Reactivity toward NO and O₂

NO Decomposition Activated by Preadsorption of O₂ onto Copper Cluster Anions