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The Quest for Stability: Structural Dependence of Rh(111) on Oxygen Coverage at Elevated Temperature

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Department of Chemistry & Biochemistry, Loyola University Chicago, 1068 West Sheridan Road, Chicago, Illinois 60660, United States
Department of Chemistry and Biochemistry, The University of Tulsa, 800 South Tucker Drive, Tulsa, Oklahoma 74104, United States
*D. R. Killelea. E-mail address: [email protected]. Ph: (773) 508-3136.
Cite this: J. Phys. Chem. C 2017, 121, 19, 10470–10475
Publication Date (Web):May 1, 2017
https://doi.org/10.1021/acs.jpcc.7b02738
Copyright © 2017 American Chemical Society

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    Abstract

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    Recent studies have shown the importance of oxide surfaces in heterogeneously catalyzed reactions. Because of the difficulties in reproducibly preparing oxidized metal surfaces, it is often unclear what species are thermodynamically stable and what factors effect the oxide formation process. In this work, we show that the thermodynamically stable phases on Rh(111) after exposure to atomic oxygen are the (2×1)-O adlayer and the trilayer surface oxide, RhO2. Formation of RhO2 was facilitated by surface defects and elevated concentrations of dissolved O atoms in the subsurface region. As the concentration of subsurface O atoms decreased, the coverage of RhO2 decreased so that only the (2×1)-O adlayer was present on the surface. The importance of subsurface oxygen species in RhO2 formation and stability indicates a complex relationship between surface structure and subsurface oxygen concentration.

    Cited By

    This article is cited by 9 publications.

    1. Carson J. Mize, Lonnie D. Crosby, Sara B. Isbill, Sharani Roy. Insight into Subsurface Adsorption Derived from a Lattice-Gas Model and Monte Carlo Simulations. The Journal of Physical Chemistry C 2022, 126 (11) , 5343-5353. https://doi.org/10.1021/acs.jpcc.2c00342
    2. Zdeněk Rafaj, Jozef Krutel, Václav Nehasil. Oxygen Exchange between Catalyst and Active Support during CO Oxidation on Rh/CeO2(111) and Rh/CeO2(110): Isotope Labeled 18O Study. The Journal of Physical Chemistry C 2021, 125 (29) , 15959-15966. https://doi.org/10.1021/acs.jpcc.1c04146
    3. Marie E. Turano, Elizabeth A. Jamka, Maxwell Z. Gillum, K. D. Gibson, Rachael G. Farber, Weronika Walkosz, S. J. Sibener, Richard A. Rosenberg, Daniel R. Killelea. Emergence of Subsurface Oxygen on Rh(111). The Journal of Physical Chemistry Letters 2021, 12 (25) , 5844-5849. https://doi.org/10.1021/acs.jpclett.1c01820
    4. Rachael G. Farber, Marie E. Turano, Daniel R. Killelea. Identification of Surface Sites for Low-Temperature Heterogeneously Catalyzed CO Oxidation on Rh(111). ACS Catalysis 2018, 8 (12) , 11483-11490. https://doi.org/10.1021/acscatal.8b03887
    5. Arved C. Dorst, Friedrich Güthoff, Daniel Schauermann, Alec M. Wodtke, Daniel R. Killelea, Tim Schäfer. Velocity map images of desorbing oxygen from sub-surface states of Rh(111). Physical Chemistry Chemical Physics 2022, 24 (43) , 26421-26427. https://doi.org/10.1039/D2CP03369K
    6. Elizabeth A. Jamka, Maxwell Z. Gillum, Christina N. Grytsyshyn-Giger, Faith J. Lewis, Daniel R. Killelea. Temperature-resolved surface infrared spectroscopy of CO on Rh(111) and (2 × 1)-O/Rh(111). Journal of Vacuum Science & Technology A 2022, 40 (4) https://doi.org/10.1116/6.0001932
    7. P. Winkler, J. Zeininger, Y. Suchorski, M. Stöger-Pollach, P. Zeller, M. Amati, L. Gregoratti, G. Rupprechter. How the anisotropy of surface oxide formation influences the transient activity of a surface reaction. Nature Communications 2021, 12 (1) https://doi.org/10.1038/s41467-020-20377-9
    8. Marie E. Turano, Rachael G. Farber, George Hildebrandt, Daniel R. Killelea. Temperature dependence of CO oxidation on Rh(111) by adsorbed oxygen. Surface Science 2020, 695 , 121573. https://doi.org/10.1016/j.susc.2020.121573
    9. Jesse A. Phillips, K.P. Boyd, I. Baljak, L.K. Harville, Erin V. Iski. Formation of magic gold fingers under mild and relevant experimental conditions. Surface Science 2019, 687 , 1-6. https://doi.org/10.1016/j.susc.2019.04.005

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