Kinetic and Mechanistic Studies of Intercalation in Lamellar Hosts Using Time‐Resolved X‐Ray Diffraction

Abstract

AbstractEnergy dispersive X‐ray diffraction (EDXRD) has been used to perform in‐situ kinetic studies on the intercalation of a range of guest molecules in layered lattices. The kinetics of the intercalation of cations {K+, PyH+ (Py = C5H5N), NMe+4} and the long chain ammonium ions C12TMA, C16TMA, C18TMA (C12TMA = dodecyltrimethylammonium, C16TMA = hexadecyltrimethylammonium and C18TMA = octadecyltrimethylammonium) into crystals of MnPS3 have been determined. These reactions are very fast and in some cases novel transient phases are observed. The rate of cobaltocene, Co(η‐C5H5)2, intercalation in layered dichalcogenides ZrS2, 2H‐SnS2, 2H‐SnSe2, 2H‐TaS2, 2H‐NbS3, 1T‐TaS2 and TiS2 has also been investigated. Integrated intensities of the Bragg reflections have been used to determine the extent of reaction, (α), versus time for each of these reactions. A number of kinetic models have been considered, including the Avrami‐Erofeyev (m = 1.5) deceleratory nuclei‐growth model and statistical simulation. The concentration and solvent dependence of the rate of Co(η‐C5H5)2 intercalation into 2H‐SnS2 has also been determined. Surprisingly we find that the rate of intercalation is invariant to the initial Co(η‐C5H5)2 concentration over a wide concentration range.