Differences in Molecular Adsorption Emanating from the (2 × 1) Reconstruction of Calcite(104)

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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2023-02-23

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en

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7

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Journal of Physical Chemistry Letters, Volume 14, issue 7, pp. 1983-1989

Abstract

Calcite, in the natural environment the most stable polymorph of calcium carbonate (CaCO3), not only is an abundant mineral in the Earth’s crust but also forms a central constituent in the biominerals of living organisms. Intensive studies of calcite(104), the surface supporting virtually all processes, have been performed, and the interaction with a plethora of adsorbed species has been studied. Surprisingly, there is still serious ambiguity regarding the properties of the calcite(104) surface: effects such as a row-pairing or a (2 × 1) reconstruction have been reported, yet so far without physicochemical explanation. Here, we unravel the microscopic geometry of calcite(104) using high-resolution atomic force microscopy (AFM) data acquired at 5 K combined with density functional theory (DFT) and AFM image calculations. A (2 × 1) reconstruction of a pg-symmetric surface is found to be the thermodynamically most stable form. Most importantly, a decisive impact of the (2 × 1) reconstruction on adsorbed species is revealed for carbon monoxide.

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Funding Information: German Research Foundation grant RA2832/1-1 (P.R., J.H.); Universität Osnabrück, Innovationspool (P.R., J.H.); World Premier International Research Center Initiative (WPI), MEXT, Japan (ASF); Academy of Finland project no. 314862 (Y.S.R., O.K., A.S.F.). Publisher Copyright: © 2023 American Chemical Society.

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Heggemann, J, Ranawat, Y S, Krejčí, O, Foster, A S & Rahe, P 2023, ' Differences in Molecular Adsorption Emanating from the (2 × 1) Reconstruction of Calcite(104) ', Journal of Physical Chemistry Letters, vol. 14, no. 7, pp. 1983-1989 . https://doi.org/10.1021/acs.jpclett.2c03243