Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: A ⁶Li MAS NMR study of adsorption and absorption on goethite

High-resolution ²H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (β-FeOOH, particle size ≈ 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, the system representing an ideal model system for NMR studies. 6Li resonances with large hyperfine shifts (approximately 145 ppm) were observed above the goethite point of zero charge, providing clear evidence for the presence of Li-O-Fe connectivities, and thus the formation of an inner sphere Li ⁺ complex on the goethite surface. Even larger Li hyperfine shifts (289 ppm) were observed for Li ⁺-exchanged goethite, which contains lithium ions in the tunnels of the goethite structure, confirming the Li assignment of the 145 ppm Li resonance to the surface sites.