• Open Access

On the Origin of the Surprisingly Sluggish Redox Reaction of the N2O/CO Couple Mediated by [Y2O2]+. and [YAlO2]+. Cluster Ions in the Gas Phase

Authors

  • Jia-Bi Ma,

    1. Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany)
    2. State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, 100190 Beijing (People's Republic of China)
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  • Dr. Zhe-Chen Wang,

    1. Department of Chemistry, Colorado State University, Fort Collins, CO 80526 (USA)
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  • Dr. Maria Schlangen,

    Corresponding author
    1. Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany)
    • Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany)
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  • Prof. Dr. Sheng-Gui He,

    Corresponding author
    1. State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, 100190 Beijing (People's Republic of China)
    • State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, 100190 Beijing (People's Republic of China)
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  • Prof. Dr. Helmut Schwarz

    Corresponding author
    1. Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany)
    2. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)
    • Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin (Germany)
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  • This work was supported by the Fonds der Chemischen Industrie, the Deutsche Forschungsgemeinschaft (DFG), and the Cluster of Excellence “Unifying Concepts in Catalysis” (coordinated by the Technische Universität Berlin and funded by the DFG). For computational resources, the Institut für Mathematik at the Technische Universität Berlin is acknowledged. We thank Dr. Burkhard Butschke and Nicolas Dietl for helpful suggestions.

Abstract

original image

Kinetic energy barriers that have entirely different origins are the reasons for the impedance of the catalytic N2O/CO redox cycle mediated by both [YAlO2]+. and [Y2O2]+. clusters (see scheme). While oxidation with N2O is the bottleneck for [YAlO2]+., oxidation of [Y2O2]+. with N2O is possible, but reduction of [Y2O3]+. by CO is prevented. This arises because of “doping” effects which can control local charges and spin distributions.

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