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Thermodynamics of H2O Splitting and H-2 Formation at the Cu(110)-Water Interface
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Technology.ORCID iD: 0000-0002-0086-5536
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Materials Technology.ORCID iD: 0000-0002-9920-5393
2015 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 25, 14102-14113 p.Article in journal (Refereed) Published
Abstract [en]

We used density functional theory to investigate the sequential oxidation of the (110) surface of fcc copper triggered by the dehydrogenation of molecularly adsorbed water the reactions studied did not involve any oxygen besides that present in the water molecules. According to the obtained Gibbs free energies, the formation of half a inonolayer of HO and the corresponding amount of hydrogen gas is spontaneous (Delta(r)G(0) < 0) starting from a monolayer of adsorbed water at Cu(110) The subsequent dehydrogenation steps necessary to ultimately form one monolayer of O atoms are nonspontaneous (Delta(r)G(o) > 0). We present a computationally efficient approach which shows good accuracy for determining the solvation energy of the Cu(110) surface, deviating only by 0.014 eV from literature data. The solvation effect imparts additional stabilization to several oxygen-containing species adsorbed at the Cu(110) surface. Additionally, we investigated the effect of an overlayer of water molecules at the surface where the dehydrogenation of H2O takes place. We found that even though the Gibbs free energy changes associated with the first steps of dehydrogenation of H2O at the Cu surface do not differ substantially from those without an additional water layer, subsequent dehydrogenation steps are favored by as much as 1.6 eV. In view of these results we discuss the importance of the hydrogen-bonding network formed when an overlayer of H2O is present in determining the reactivity of surface species. Additionally, we found a considerable effect of the second water layer on the surface relaxation, which differs significantly from the case where no second water layer is present. The hydrogen-bonding network has an important role in affecting the chemistry of the surface species but also in stabilizing the surface itself, which in turn affects the surface relaxation. These findings shed additional light on the modeling of surface processes in solution, which have implications for corrosion science and catalysis.

Place, publisher, year, edition, pages
2015. Vol. 119, no 25, 14102-14113 p.
National Category
Materials Engineering
URN: urn:nbn:se:kth:diva-171290DOI: 10.1021/acs.jpcc.5b01154ISI: 000357140500014ScopusID: 2-s2.0-84933056918OAI: diva2:843234

QC 20150728

Available from: 2015-07-28 Created: 2015-07-27 Last updated: 2015-07-28Bibliographically approved

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Lousada, Claudio MiguelKorzhavyi, Pavel A
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