KINETIC AND MECHANISTIC STUDIES OF INTERCALATION IN LAMELLAR HOSTS USING TIME-RESOLVED X-RAY-DIFFRACTION

Energy dispersive X-ray diffraction (EDXRD) has been used to perform i n-situ kinetic studies on the intercalation of a range of guest molecu les in layered lattices. The kinetics of the intercalation of cations {K+, PyH+ (Py = C5H5N), NMe4+} and the long chain ammonium ions C(12)T MA, C(16)TMA, C(18)TMA (C(12)TMA = dodecyltrimethylammonium, C(16)TMA = hexadecyluimethylapunonium and C(18)TMA = octadecyltrimethylammonium ) into crystals of MnPS3 have been determined. These reactions are ver y fast and in some cases novel transient phases are observed. The rate of cobaltocene, Co(eta-C5H5)(2), intercalation in layered dichalcogen ides ZrS2, 2H-SnS2, 2H-SnSe2, 2H-TaS2, 2H-NbS2, IT-TaS2 and TiS2 has a lso been investigated. Integrated intensities of the Bragg reflections have been used to determine the extent of reaction, (ol), versus time for each of these reactions. A number of kinetic models have been con sidered, including the Avrami Erofeyev (m = 1.5) deceleratory nuclei-g rowth model and statistical simulation. The concentration and solvent dependence of the rate of Co(eta-C5H5)(2) intercalation into 2H-SnS2 h as also been determined. Surprisingly we find that the rate of interca lation is invariant to the initial Co(eta-C5H5)(2) concentration over a wide concentration range.