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Application of the surface potential data to elucidate interfacial equilibrium at ceria/aqueous electrolyte interface

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Abstract

Interfacial properties of ceria (CeO2) nanoparticles and highly organized ceria crystal planes {111} and {100} in the aqueous electrolyte solution were studied. It was confirmed by high resolution electron spectroscopy that a primary ceria nanoparticle consists mostly of two crystal planes {111} and {100} with different surface sites exposed to the aqueous electrolyte solution. Interfacial properties of ceria nanoparticles are directly related to the reactivity and surface densities of existing surface sites. However, surface characterization (potentiometric titrations and electrophoretic measurements) provides only some kind of average surface properties i.e. average surface charge densities and surface potentials. The point of zero charge (pHpzc) of ceria nanoparticles was measured to be between 6.4 and 8.7, depending on the electrolyte concentration, and the isoelectric point at pHiep = 6.5. With the purpose of understanding ceria nanoparticles surface charging the inner surface potentials of ceria macro crystal planes {111} and {100} were measured for the first time, by means of single crystal electrodes, as a function of pH and ionic strength. The inner surface potential directly affects the state of ionic species bound to a certain surface plane and is thus an essential parameter governing interfacial equilibrium. From the measured Ψ 0(pH) data and applying the Multi Site Complexation Model the thermodynamic equilibrium constants of doubly-coordinated ≡Ce2-OH (at the {100} ceria crystal plane) as well as singly-coordinated ≡Ce1-OH and triply-coordinated ≡Ce3-OH (at the {111} ceria crystal plane) were evaluated. The Ψ 0(pH) function differs for two examined ceria planes, however the inner surface potentials of both planes depend on ionic strength having a broad electroneutrality region between pH = 6 and pH = 9.

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Acknowledgments

This work has been supported by Croatian Science Foundation under the project (IP-2014-09-6972) and by Croatian Academy of Sciences and Arts under the project “Surface properties of cerium oxide nanoparticles in aqueous electrolyte solutions”. The authors are grateful to the Laboratory for Precipitation Processes, Ruđer Bošković Institute (Zagreb, Croatia) for BET measurements, and dr. Dominik Cinčić (Department of Chemistry, Faculty of Science, University of Zagreb) for powder X-ray diffraction measurements.

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Authors and Affiliations

  1. Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000, Zagreb, Croatia

    Danijel Namjesnik & Tajana Preočanin

  2. Pliva Croatia Ltd., Research and Development, Prilaz baruna Filipovića 25, HR-10000, Zagreb, Croatia

    Sanela Mutka

  3. Division of Chemistry and Biochemistry, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000, Zagreb, Croatia

    Damir Iveković

  4. Division of Materials Physics, Ruđer Bošković Institute, Zagreb, Bijenička c. 54, HR-10000, Zagreb, Croatia

    Andreja Gajović

  5. Fritz-Haber-Institute der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany

    Marc Willinger

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  1. Danijel Namjesnik
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Correspondence to Tajana Preočanin.

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Namjesnik, D., Mutka, S., Iveković, D. et al. Application of the surface potential data to elucidate interfacial equilibrium at ceria/aqueous electrolyte interface. Adsorption 22, 825–837 (2016). https://doi.org/10.1007/s10450-016-9785-x

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