Drying Molybdate/Iron Hydroxide Interface Leading to Both Inner- and Outer-Sphere Surface Complexes Depending on Initial Concentrations

Drying is ubiquitous. However, its influence on surface speciation has been seldom studied. Through an in situ Attenuated Total Reflection–Infrared (ATR-IR) spectroscopy analysis of the drying of molybdate solutions on a lepidocrocite particle film, the change in surface speciation is followed. No formation polymolybdates nor precipitate are observed upon drying at pH 8. An in situ washing of the dried solid/solution interface unveils the existence of surface outer-sphere and inner-sphere complexes. Decreasing the molybdate concentration highlights a saturation effect of the surface upon drying. Moreover, the careful analysis of substrate IR bands showed non-uniform drying which is an important insight to understand dehydration chemistry. The remaining molybdate ions at the surface as inner-sphere complexes are present as binuclear monodentate complexes stabilized by sodium.