Local Environments of Li in the Interlayer of Clay Minerals at Room and High Temperatures

We used and MAS NMR to investigate the fate and local environments of Li in the interlayer of clay minerals such as hectorite, Woming-montmorillonite, beidellite, and lepidollite at room and high () temperature. Although NMR spectra show narrower peaks than those of NMR, S/N ratio is low and there are no obvious differences in chemical shifts suggesting that it is difficult to apply NMR to have information on the local environments of Li in the clay interlayers. NMR spectra, however, show changes in the peak width and quadrupole patterns providing information on the local environments of Li in the interlayer even though changes in the chemical shift are not observed. In montmorillonite, two different local environments of Li are observed; one has a narrow peak with typical quadrupole patterns whereas another has a broad peak without those of the patterns. Changes in the peak width is also observed from broad to narrow in the NMR spectra for beidellite but not for hectorite at high temperature. Our results suggest that the peak width change in the broad peak is attributed to the coordination changes in the water molecules around Li which is tightly bonded on the basal oxygen of Si tetrahedra as inner-sphere complexes. The narrow peak in montmorillnoite can be assigned to the Li bended as outer-sphere complexes.