Atomic-Scale Studies of Fe3 O4 (001) and TiO2 (110) Surfaces Following Immersion in CO2 -Acidified Water.

Difficulties associated with the integration of liquids into a UHV environment make surface-science style studies of mineral dissolution particularly challenging. Recently, we developed a novel experimental setup for the UHV-compatible dosing of ultrapure liquid water and studied its interaction with TiO2 and Fe3 O4 surfaces. Herein, we describe a simple approach to vary the pH through the partial pressure of CO2 ( p C O 2 ) in the surrounding vacuum chamber and use this to study how these surfaces react to an acidic solution. The TiO2 (110) surface is unaffected by the acidic solution, except for a small amount of carbonaceous contamination. The Fe3 O4 (001)-( 2 × 2 )R45° surface begins to dissolve at a pH 4.0-3.9 ( p C O 2 =0.8-1 bar) and, although it is significantly roughened, the atomic-scale structure of the Fe3 O4 (001) surface layer remains visible in scanning tunneling microscopy (STM) images. X-ray photoelectron spectroscopy (XPS) reveals that the surface is chemically reduced and contains a significant accumulation of bicarbonate (HCO3 - ) species. These observations are consistent with Fe(II) being extracted by bicarbonate ions, leading to dissolved iron bicarbonate complexes (Fe(HCO3 )2 ), which precipitate onto the surface when the water evaporates.