Fe(II) adsorption on hematite (0 0 0 1)

The surface structure of α-Fe2O3(0 0 0 1) was studied using crystal truncation rod (CTR) X-ray diffraction before and after reaction with aqueous Fe(II) at pH 5. The CTR results show the unreacted α-Fe2O3(0 0 0 1) surface consists of two chemically distinct structural domains: an O-layer terminated domain and a hydroxylated Fe-layer terminated domain. After exposing the α-Fe2O3(0 0 0 1) surface to aqueous Fe(II), the surface structure of both co-existing structural domains was modified due to adsorption of Fe at crystallographic lattice sites of the substrate, resulting in six-coordinated adsorbed Fe at the surface. The average Fe–O bond lengths of the adsorbed Fe are consistent with typical Fe(III)–O bond lengths (in octahedral coordination), providing evidence for the oxidation of Fe(II) to Fe(III) upon adsorption. These results highlight the important role of substrate surface structure in controlling Fe(II) adsorption. Furthermore, the molecular scale structural characterization of adsorbed Fe provides insight into the process of Fe(II) induced structural modification of hematite surfaces, which in turn aids in assessing the effective reactivity of hematite surfaces in Fe(II) rich environments.