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Size-dependent reactivity of Rh cationic clusters to reduce NO by CO in the gas phase at high temperatures
Ken Miyajima1, Toshiaki Nagata1, Fumitaka Mafuné1
1Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8902, Japan. mafune@cluster.c.u-tokyo.ac.jp.
Abstract:
The reactivity of the reduction of NO pre-adsorbed on Rh2-9+ clusters by CO was investigated using a combination of an alternate on-off gas injection method and thermal desorption spectrometry. The reduction of RhNO+ clusters by CO was evaluated by varying the CO concentration at T = 903 K. Among the RhNO+ clusters, the Rh3N2O2+ cluster exhibited the highest reduction activity, whereas the other clusters, Rh2,4-9NO+, showed lower reactivity. Density functional theory (DFT) calculations for Rh3+ and Rh6+ revealed that the rate-determining step for NO reduction in the presence of CO was NO bond dissociation through the kinetics analysis using the RRKM theory. The reduction of Rh3N2O2+ is kinetically preferable to that of Rh6N2O2+. The DFT results were in qualitative agreement with the experimental results.
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