Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters

Literature Information

Publication Date 2012-02-02
DOI 10.1039/C2CP24036J
Impact Factor 3.676
Authors

Akira Yamada, Ken Miyajima, Fumitaka Mafuné


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Abstract

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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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