Effect of Dehydration on Sulfate Coordination and Speciation at the Fe−(Hydr)oxide−Water Interface: A Molecular Orbital/Density Functional Theory and Fourier Transform Infrared Spectroscopic Investigation

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Abstract
The effect of dehydration on the coordination and speciation of sulfate at the Fe−(hydr)oxide−H2O interface was investigated using molecular orbital/density functional theory (MO/DFT) and Fourier transform infrared (FTIR) spectroscopy. IR frequency calculations were performed at the UB3LYP/6-31+G(d) level of theory for potential sulfate (bidentate bridging, monodentate, and H-bonded) and bisulfate (bidentate bridging and monodentate) surface complexes. MO/DFT calculated IR frequencies were compared to available IR literature results and attenuated total reflectance (ATR) FTIR spectra collected in our laboratory of sulfate adsorbed at the hematite−H2O interface. IR frequency calculations performed using the larger 6-311+G(d,p) basis set resulted in minor frequency shifts that did not dramatically alter the agreement with experiment. This investigation proposes that sulfate undergoes a speciation change as a function of surface dehydration. A generalized model for the speciation change is proposed as follows. (1) At the Fe−(hydr)oxide−H2O interface, sulfate adsorbs as a bidentate bridging or monodentate surface complex under most experimental conditions. (2) Upon surface dehydration, sulfate changes speciation to form bidentate bridging and/or monodentate bisulfate. However, surface dehydration does not yield 100% speciation change but leads to a mixture of sulfate and bisulfate. (3) The speciation change is reversible as a function of rehydration. The reversibility of the sulfate−bisulfate speciation change is chiefly determined by the local hydration environment of the O−H bond in bisulfate. Under dehydrated conditions, the O−H bond length is approximately 0.98 Å. The bond length substantially increases (bond strength decreases) to approximately 1.03 Å when the initial H-bond network is re-established through hydration, likely leading to deprotonation upon full mineral surface hydration.

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