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Kinetic and Mechanistic Studies of Intercalation in Lamellar Hosts Using Time‐Resolved X‐Ray Diffraction
Author(s) -
O'Hare Dermot,
Evans John S. O.,
Price Stephen
Publication year - 1998
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199800089
Subject(s) - intercalation (chemistry) , chemistry , lamellar structure , crystallography , kinetic energy , atmospheric temperature range , cobaltocene , kinetics , x ray crystallography , diffraction , molecule , inorganic chemistry , thermodynamics , organic chemistry , electrochemistry , physics , ferrocene , electrode , quantum mechanics , optics
Energy 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 = C 5 H 5 N), NMe + 4 } and the long chain ammonium ions C 12 TMA, C 16 TMA, C 18 TMA (C 12 TMA = dodecyltrimethylammonium, C 16 TMA = hexadecyltrimethylammonium and C 18 TMA = octadecyltrimethylammonium) into crystals of MnPS 3 have been determined. These reactions are very fast and in some cases novel transient phases are observed. The rate of cobaltocene, Co(η‐C 5 H 5 ) 2 , intercalation in layered dichalcogenides ZrS 2 , 2H‐SnS 2 , 2H‐SnSe 2 , 2H‐TaS 2 , 2H‐NbS 3 , 1T‐TaS 2 and TiS 2 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‐C 5 H 5 ) 2 intercalation into 2H‐SnS 2 has also been determined. Surprisingly we find that the rate of intercalation is invariant to the initial Co(η‐C 5 H 5 ) 2 concentration over a wide concentration range.