Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters
Literature Information
Akira Yamada, Ken Miyajima, Fumitaka Mafuné
Gas phase catalytic reactions involving the reduction of N2O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rhn (n = 10–28), using mass spectrometry. Sequential oxygen transfer reactions, RhnOm−1 + N2O → RhnOm + N2 (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, RhnOm + CO → RhnOm−1 + CO2 (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N2O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around RhnOm (m ≥ 4) than around bare Rhn. Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalyticCO oxidation reaction on a rhodium surface.
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