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Density functional theory study of water adsorption on FeOOH surfaces

Surface Science 606(21–22): 1623-1632

Autoren/Herausgeber: Otte K
Schmahl WW
Pentcheva R
Erschienen: 2012
Using density functional theory (DFT) calculations with an on-site Coulomb repulsion term, we study the composition, stability, and electronic properties of the most common FeOOH surfaces goethite(101), akaganeite(100), and lepidocrocite(010), and their interaction with water. Despite the differences in surface structure, the trends in surface stability of these FeOOH polymorphs exhibit remarkable similarities. We find that the reactivity and the binding configuration of adsorbates depend strongly on the coordination of surface iron: at the fourfold coordinated Fe2 site water is chemisorbed, whereas at the fivefold coordinated Fe1 water is only loosely bound with hydrogen pointing towards the surface. Our results show that the oxidation state of surface iron can be controlled by the surface termination where ferryl (Fe4 +) species emerge for oxygen terminated surfaces and ferrous iron (Fe2 +) at iron and water terminations leading to a reduced band gap. In contrast, the fully hydroxylated surfaces, identified as stable surface configurations at standard conditions from the surface phase diagram, show electronic properties and band gaps closest to bulk FeOOH with ferric surface iron (Fe3 +). Only in the case of goethite(101), a termination with mixed surface hydroxyl and aquo groups is stabilized.

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