Browse > Article

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

Kim, Yeong-Kyoo (Department of Geology, Kyungpook National University)
Lee, Ji-Eun (Department of Geology, Kyungpook National University)
Publication Information
Journal of the Mineralogical Society of Korea / v.20, no.3, 2007 , pp. 193-201 More about this Journal
Abstract
We used $^6Li$ and $^7Li$ 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 ($250^{\circ}C$) temperature. Although $^6Li$ NMR spectra show narrower peaks than those of $^7Li$ NMR, S/N ratio is low and there are no obvious differences in chemical shifts suggesting that it is difficult to apply $^6Li$ NMR to have information on the local environments of Li in the clay interlayers. $^7Li$ 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 $^7Li$ 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.
Keywords
$^6Li$ NMR; $^7Li$ NMR; hectorite; montmorillonite; beidellite; clay interlayer;
Citations & Related Records
연도 인용수 순위
  • Reference
1 Greene-Kelly, R. (1953) Irreversible dehydration in montmorillonite: II. Clay Min. Bull. 2, 52-56   DOI
2 Kim, Y., Kirkpatrick, R.J. and Cygan, R.T. (1996b) $^{133}Cs$ NMR Study of Cs on the surfaces of kaolinite and illite. Geochim. Cosmochim. Acta, 60, 4059-4074   DOI   ScienceOn
3 Laperche, V., Lambert, J.F., Prost, R. and Fripiat, J.J. (1990) High-resolution solid-state NMR of exchangeable cations in the interlayer surface of a swelling mica: $^{23}Na$, $^{111}Cd$, and $^{133}Cs$ vermiculites. J. Phys. Chem., 94, 8821-8831   DOI
4 Luca, V., Cardile, C.M. and Meinhold, R.H. (1989) High-resolution multinuclear NMR study of cation migration in montmorillonite. Clay Mineral., 24, 115-119   DOI
5 Weiss, C.A. Jr., Kirkpatrick, R.J. and Altaner, S.P. (1990a) The structural environment of cations adsorbed onto clays: $^{133}Cs$ variable- temperature MAS NMR spectroscopic study of hectorite. Geochim. Cosmochim. Acta, 54, 1655-1669   DOI   ScienceOn
6 Jaynes, W.F. and Bigham, J.M. (1987) Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites. Clays Clay. Miner., 35, 440-448   DOI
7 Tinet, D., Faugere, A.M. and Prost, R. (1991) $^{111}Cd$ NMR chemical shift tensor analysis of cadmium-exchanged clays and clay gels. J. Phys. Chem. 95, 8804-8807   DOI
8 Greathouse, J. and Sposito, G. (1998) Monte Carlo and molecular dynamics studies of interlayer structure in $Li(H_2O)_3$-smectite. J. Phys. Chem. B, 102, 2406-2414   DOI   ScienceOn
9 Hofmann, U. and Klemen, R. (1950) Verlust der Austauschfahigkeit von Lithiumionen an Bentonit durch Erhitzung. Z. anort. allgem Chem., 262, 95-99
10 Lambert, J-F., Prost, R. and Smith, M.E. (1992) $^{39}K$ solid-state NMR studies of potassium tecto- and phyllosilicates: The in situ detection of hydratable $K^+$ in smectites. Clays Clay Mineral., 40, 253-261   DOI
11 Calvet, R. and Prost, R. (1971) Cation migration into empty octahedral sites and surface properties of clays. Clays Clay Mineral., 19, 175-150   DOI
12 Quirk, J.P. and Theng, B.K.G. (1960) Effect of surface density of charge on the physical swelling of lithium montmorillonite. Nature, 187, 967-968   DOI
13 Tettenhorst, R. (1962) Cation migration in montmorillonite. Amer. Mineral., 47, 769-773
14 Xu, Z. and Stebbins, J.F. (1995) $^6Li$ nuclear magnetic resonance chemical shift, coordination number, and relaxation in crystalline and glassy silicates. Solid State Nucl. Mag. Reson., 5, 103-112   DOI   ScienceOn
15 Weiss, C.A. Jr., Kirkpatrick, R.J. and Altaner, S.P. (1990b) Variations in interlayer cation sites of clay minerals as studied by $^{133}Cs$ MAS nuclear magnetic resonance spectroscopy. Am. Mineral., 75, 970-982
16 Bank, S., Bank, J.F. and Ellis, P.D. (1989) Solid-state $^{113}Cd$ nuclear magnetic resonance study of exchanged montmorillonites. J. Phys. Chem., 93, 4847-4855   DOI
17 Kim, Y., Cygan, R.T. and Kirkpatrick, R.J. (1996a) $^{133}Cd$ NMR and XPS investigation of Cs adsorbed on clay minerals and related phases. Geochim. Cosmochim. Acta. 60, 1041-1052   DOI   ScienceOn
18 Theng, B.K.G., Hayashi, S., Soma, M. and Seyama, H. (1997) Nuclear mganetic resonance and X-ray photoelectron spectroscopic investigation of lithium migration in montmorillonite. Clays Clay Mineral., 45, 718-723   DOI
19 Alvero, R., Alba, M.D., Castro, M.A. and Trillo, J.M. (1994) Reversible migration of lithium in montmorillonites. J. Phys. Chem., 98, 7848-7853   DOI   ScienceOn
20 Kim, Y. and Kirkpatrick, R.J. (1997) $^{23}Na$ and $^{133}Cs$ NMR study of cation adsorption on mineral surfaces: Local environments, dynamics, and effects of mixed cations. Geochim. Cosmochim. Acta, 61, 5199-5208   DOI   ScienceOn