Decomposition of nitric oxide by rhodium cluster cations at high temperatures
文献情報
Toshiaki Nagata, Kimihiro Kawada, Xuemei Chen, Masato Yamaguchi, Ken Miyajima, Fumitaka Mafuné
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.
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