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Issue 30, 2017
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Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study

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Abstract

Hydration reactions on a carbonate-terminated cubic ZrO2(110) surface were analyzed using ab initio molecular dynamics (AIMD) simulations. After hydration reactions, carbonates were still present on the surface at 500 K. However, these carbonates are very weak conjugate bases and only act as steric hindrance in proton hopping processes between acidic chemisorbed H2O molecules (Zr–OH2) and monodentate hydroxyl groups (Zr–OH). Similar to a carbonate-free hydrated surface, Zr–OH2, Zr–OH, and polydentate hydroxyl groups ([double bond splayed left]OH+) were observed, while the ratio of acidic Zr–OH2 was significantly larger than that on the carbonate-free hydrated surface. A thermodynamic discussion and bond property analysis reveal that CO2 adsorption significantly decreases the basicity of surface oxide ions ([double bond splayed left]O), whereas the acidity of Zr–OH2 is not affected. As a result, protons released from [double bond splayed left]OH+ react with Zr–OH to form Zr–OH2, leading to a deficiency of proton acceptor sites, which decreases the proton conductivity by the hopping mechanism.

Graphical abstract: Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study

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Publication details

The article was received on 15 Mar 2017, accepted on 03 Jul 2017 and first published on 03 Jul 2017


Article type: Paper
DOI: 10.1039/C7CP01650F
Citation: Phys. Chem. Chem. Phys., 2017,19, 20198-20205
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    Effects of CO2 adsorption on proton migration on a hydrated ZrO2 surface: an ab initio molecular dynamics study

    R. Sato, Y. Shibuta, F. Shimojo and S. Yamaguchi, Phys. Chem. Chem. Phys., 2017, 19, 20198
    DOI: 10.1039/C7CP01650F

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