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Issue 16, 2010
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Active sites of stoichiometric cerium oxide cations (CemO2m+) probed by reactions with carbon monoxide and small hydrocarbon molecules

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Abstract

Cerium oxide cluster cations (CemOn+, m = 2–16; n = 2m, 2m ± 1 and 2m ± 2) are prepared by laser ablation and reacted with carbon monoxide (CO) and small hydrocarbon molecules (CH4, C2H4, and C2H6) in a fast flow reactor. A time of flight mass spectrometer is used to detect the cluster distribution before and after the reactions. The observation of oxygen reduction and hydrogen pickup of CemO2m+ clusters strongly suggests the following reactions: (1) CemO2m+ + C2H4 → CemO2m−1+ + C2H4O (m = 2–6); (2) CemO2m+ + CO → CemO2m−1+ + CO2 (m = 4–6); and (3) CemO2m+ + CH4/C2H6 → CemO2mH+ + CH3/C2H5 (m = 2–4). Density functional theory (DFT) calculations are performed to study reaction mechanisms of Ce2O4+ + X (X = CO, CH4, C2H4, and C2H6). The calculated results are in good agreement with the experimental observations. The structural and bonding properties of CemO2m+ (m = 2–5) clusters are also investigated by the DFT calculations. The unpaired electron in each of the clusters is mainly distributed over one Ce atom (4f and 5p orbitals) and two O atoms (2p orbital) in a CeO2 moiety, which can be considered as the active site in the cluster. To further understand the nature of the active sites in CemO2m+ clusters, the fast flow reaction experiments are also carried out on zirconium oxide clusters ZrmOn+, because both Zr ([Kr]4d25s2) and Ce ([Xe]4f15d16s2) have the same number of valence electrons while the latter has one more f and one less d electrons. In addition to the oxygen transfer reactions such as ZrmO2m+ + C2H4 → ZrmO2m−1+ + C2H4O (m = 1–4) reported in the literature, hydrogen abstraction reactions ZrmO2m+ + CH4/C2H6 → ZrmO2mH+ + CH3/C2H5 are also identified. The rate constants of CO oxidation as well as hydrogen abstraction by CemO2m+ and ZrmO2m+ are very different. The reactivity and selectivity of CemO2m+versus ZrmO2m+ can be well rationalized based on the DFT calculations. The oxygen transfer and hydrogen abstraction reactions studied in this work are of widespread importance. The nature of the active sites of CemO2m+ clusters is unique and may be considered in the use and design of cerium oxide based catalysts.

Graphical abstract: Active sites of stoichiometric cerium oxide cations (CemO2m+) probed by reactions with carbon monoxide and small hydrocarbon molecules

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Publication details

The article was received on 01 Dec 2009, accepted on 22 Feb 2010 and first published on 20 Mar 2010


Article type: Paper
DOI: 10.1039/B925294K
Citation: Phys. Chem. Chem. Phys., 2010,12, 3984-3997
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    Active sites of stoichiometric cerium oxide cations (CemO2m+) probed by reactions with carbon monoxide and small hydrocarbon molecules

    X. Wu, Y. Zhao, W. Xue, Z. Wang, S. He and X. Ding, Phys. Chem. Chem. Phys., 2010, 12, 3984
    DOI: 10.1039/B925294K

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