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Structure-Dependent Dissociation of Water on Cobalt Oxide

  • Matthias Schwarz
    Matthias Schwarz
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
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    Orcidhttp://orcid.org/0000-0002-7308-3172
  • , 
  • Firas Faisal
    Firas Faisal
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
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  • , 
  • Susanne Mohr
    Susanne Mohr
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
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    Orcidhttp://orcid.org/0000-0001-6735-4477
  • , 
  • Chantal Hohner
    Chantal Hohner
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
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  • , 
  • Kristin Werner
    Kristin Werner
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
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    Orcidhttp://orcid.org/0000-0001-9540-6692
  • , 
  • Tao Xu
    Tao Xu
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
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  • , 
  • Tomáš Skála
    Tomáš Skála
    Department of Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, V Holešovičkách 2, 18000 Prague, Czech Republic
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    Orcidhttp://orcid.org/0000-0003-2909-9422
  • , 
  • Nataliya Tsud
    Nataliya Tsud
    Department of Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, V Holešovičkách 2, 18000 Prague, Czech Republic
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    Orcidhttp://orcid.org/0000-0001-7439-7731
  • , 
  • Kevin C. Prince
    Kevin C. Prince
    Elettra-Sincrotrone Trieste SCpA, Strada Statale 14, km 163.5, 34149 Basovizza-Trieste, Italy
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    Orcidhttp://orcid.org/0000-0002-5416-7354
  • , 
  • Vladimír Matolín
    Vladimír Matolín
    Department of Surface and Plasma Science, Faculty of Mathematics and Physics, Charles University, V Holešovičkách 2, 18000 Prague, Czech Republic
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  • , 
  • Yaroslava Lykhach*
    Yaroslava Lykhach
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
    *E-mail: [email protected] (Y.L.).
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    Orcidhttp://orcid.org/0000-0003-3989-0365
  • , and 
  • Jörg Libuda*
    Jörg Libuda
    Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen, Germany
    Erlangen Catalysis Resource Center and Interdisciplinary Center Interface Controlled Processes, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany
    *E-mail: [email protected] (J.L.).
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    Orcidhttp://orcid.org/0000-0003-4713-5941
Cite this: J. Phys. Chem. Lett. 2018, 9, 11, 2763–2769
Publication Date (Web):May 9, 2018
https://doi.org/10.1021/acs.jpclett.8b01033
Copyright © 2018 American Chemical Society
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    Abstract

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    Understanding the correlation between structure and reactivity of oxide surfaces is vital for the rational design of catalytic materials. In this work, we demonstrate the exceptional degree of structure sensitivity of the water dissociation reaction for one of the most important materials in catalysis and electrocatalysis. We studied H2O on two atomically defined cobalt oxide surfaces, CoO(100) and Co3O4(111). Both surfaces are terminated by O2– and Co2+ in different coordination. By infrared reflection absorption spectroscopy and synchrotron radiation photoelectron spectroscopy we show that H2O adsorbs molecularly on CoO(100), while it dissociates and forms very strongly bound OH and partially dissociated (H2O)n(OH)m clusters on Co3O4(111). We rationalize this structure dependence by the coordination number of surface Co2+. Our results show that specific well-ordered cobalt oxide surfaces interact very strongly with H2O whereas others do not. We propose that this structure dependence plays a key role in catalysis with cobalt oxide nanomaterials.

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    • Experimental details and synchrotron radiation photoelectron spectroscopy data for water adsorption at 200 K (PDF)

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