Decomposition of nitric oxide by rhodium cluster cations at high temperatures

Toshiaki Nagata, Kimihiro Kawada, Xuemei Chen, Masato Yamaguchi, Ken Miyajima, Fumitaka Mafuné

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1 Citation (Scopus)

Abstract

Decomposition reactions of NO molecules on gas-phase Rhn+ (n = 6-9) clusters were investigated by gas-phase thermal desorption spectrometry and density functional theory calculations. We found that NO adsorbs on the clusters, forming RhnNxOx+ at room temperature. Upon heating, NO desorption was observed below 800 K. Above 800 K, while for n = 7 and 8, each of Rh7N3O3+, Rh7N4O4+, and Rh8N3O3+ was found to release an N2 molecule, no N2 formation was clearly observed for Rh6,9NxOy+. We considered that both Rh7N3O3+ and Rh8N3O3+ have at least two dissociated NO molecules, while Rh6NxOx+ (x = 1-3) has one or less. Our computational results for Rh8N3O3+ suggested that the formation of an N-N bond in the Rh8N3O3+ structure must overcome an energy barrier of ∼2 eV, which is the highest among the suggested possible reaction pathways. These findings suggested that the size-dependent activity of NO decomposition is governed primarily by how NO molecules are adsorbed on Rhn+ clusters, i.e. whether two or more N atoms from dissociated NO molecules exist in the NO adsorbed clusters, and secondly, by the readiness of the N-N bond formation.

Original languageEnglish
Pages (from-to)26721-26728
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number47
DOIs
Publication statusPublished - Dec 21 2021
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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