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Pressure and Materials Effects on the Selectivity of RuO2 in NH3 Oxidation

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    Pressure and Materials Effects on the Selectivity of RuO2 in NH3 Oxidation
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    Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, HCI E 125, Wolfgang-Pauli-Strasse 10, CH-8093, Zurich, Switzerland, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007, Tarragona, Spain, and Leibniz Institute for Catalysis at the University of Rostock, Albert-Einstein-Strasse 29a, D-18059, Rostock, Germany
    * To whom correspondence should be addressed. E-mail: [email protected] (J.P.-R.), [email protected] (N.L.).
    †ETH Zurich.
    ‡Institute of Chemical Research of Catalonia (ICIQ).
    §Leibniz Institute for Catalysis at the University of Rostock.
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2010, 114, 39, 16660–16668
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp106193w
    Published September 1, 2010
    Copyright © 2010 American Chemical Society
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    Abstract

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    The pressure and materials gaps in heterogeneous catalysis often complicate the extrapolation of results from surface science experiments over single crystals to real catalysis at elevated pressures and polycrystalline samples. Previous ammonia oxidation studies reported ca. 100% NO selectivity and the absence of N2O on RuO2(110) in ultrahigh vacuum (UHV) at 530 K, p(NH3) = 10−7 mbar, and O2/NH3 = 20 (Wang, Y.; Jacobi, K.; Schone, W.-D.; Ertl, G. J. Phys. Chem. B2005, 109, 7883). Differently, our steady-state and transient experiments over polycrystalline RuO2 at ambient pressure reveal that N2 is the predominant product. The NO selectivity was as low as 6% at O2/NH3 = 2 and reached a maximum of 65% at the highest temperature (773 K) and effective oxygen-to-ammonia ratio of 140, whereas the maximum N2O selectivity was 25% at 100% NH3 conversion. Density functional theory simulations of the competing paths leading to NO, N2O, and N2 over RuO2(110) and RuO2(101) at different coverages by O- and N-containing species provided insights into the selectivity differences between the extreme operation regimes. Comparison between the (101) and (110) facets reveals that the materials effect is not likely to explain the different product distribution. Instead, the pressure effect (8 orders of magnitude higher at ambient pressure than in UHV) does. Whereas NO is formed by the direct reaction of coadsorbed N and O atoms, N2 can be formed through two different routes: direct N + N recombination or N2O decomposition. The second path is only likely at high pressures because it implies more diffusion steps of surface species, which are highly unlikely at low coverage. Thus, the main pressure effect is to facilitate alternative routes for N2 formation.

    Copyright © 2010 American Chemical Society

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    Supporting Information

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    Binding energies of intermediates as a function of the coverage for the (110) surface. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

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    This article is cited by 18 publications.

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    10. Magdalena Jabłońska. Progress on Noble Metal-Based Catalysts Dedicated to the Selective Catalytic Ammonia Oxidation into Nitrogen and Water Vapor (NH3-SCO). Molecules 2021, 26 (21) , 6461. https://doi.org/10.3390/molecules26216461
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    12. Jung Hun Shin, Geo Jong Kim, Sung Chang Hong. Reaction properties of ruthenium over Ru/TiO2 for selective catalytic oxidation of ammonia to nitrogen. Applied Surface Science 2020, 506 , 144906. https://doi.org/10.1016/j.apsusc.2019.144906
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    18. Marta Santiago, Vita A. Kondratenko, Evgenii V. Kondratenko, Núria López, Javier Pérez-Ramírez. Mechanistic analysis of direct N2O decomposition and reduction with H2 or NH3 over RuO2. Applied Catalysis B: Environmental 2011, 110 , 33-39. https://doi.org/10.1016/j.apcatb.2011.08.019
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2010, 114, 39, 16660–16668
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp106193w
    Published September 1, 2010
    Copyright © 2010 American Chemical Society
    Request reuse permissions

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