Intercalation chemistry

Intercalation reactions of solids involve the insertion of a guest species (ion or molecule) into a solid host lattice without any major rearrangement of the solid 

Graphite (K vapour or melt) CgK CgK (bronze) C24K (steel blue) 

Essentials of Inorganic Materials Synthesis, First Edition. C.N.R. Rao and Kanishka Biswas. 2015 John Wiley Sons, Inc. Published 2015 by John Wiley Sons, Inc. 

FIGURE 10.2.1 Staging in intercalation compounds (schematic). Guest molecules are represented by circles in between the layers (shown by lines). 

Redox intercalation reactions (e.g. Li,TiS2 where the lithium metal reduces the TiS layers) can be written as 

Reactions between certain solids possessing layered structures (e.g. graphite, silicates, metal dichalcogenides such as TaS2) and Lewis bases such as ammonia and pyridine, forming intercalation compounds, are discussed in the next section. 

Intercalation refers to a solid state reaction involving reversible insertion of guest species G into a host structure [Hs]. The host provides an interconnected system of accessible unoccupied sites, . The reaction can be schematically represented as 

In addition to graphite, a wide variety of inorganic solids such as layered 

In the presence of liquid HF, graphite is found to be reversibly intercalated by fluorine. First-stage materials have the composition Ci2(HF)F (l n 5), and the ultimate salt is the second-stage bifluoride C,2HF2. Extensive studies on these intercalates by Mallouk et al, (1985) have shown conductivities ranging from the metallic to the insulator regime. 

One of the biggest mistakes made in conceptualizing polymer nanocomposites is in the relative sizes of the polymer and clay plates. It is common to see schematic representations of wavy polymer molecules that are much longer than the clay plates. This picture is quite misleading and can lead to incorrect interpretation of data. In fact, the normal commercially available montmorillonite has a long dimension in the 

---

Rosseinsky M J 1995 Fullerene intercalation chemistry J. Mater. Chem. 5 1497... 

Intercalation chemistry electron/ion transfer reactions. R. Schollhom, Comments Inorg. Chem.,... 

Whittingham MS (1979) Intercalation chemistry and energy storage. J Solid State Chem 29 303-310... 

Whittinfdtam, M.S. Jacobson, A.J. Eds. "Intercalation Chemistry" Academic Press, New York, 1982. 

Trasatti, S. (Ed.), Electrodes of Conductive Oxides, Elsevier, Amsterdam, 1980. Vincent, C. A., F. Bonino, M. Lazari, and B. Scrosati, Modern Batteries, An Introduction to Electrochemical Power Sources, E. Arnold, London, 1984. Whittingham M. S., and N. G. Jacobson, Intercalation Chemistry, Academic Press, Orlando, 1982. 

Clearfield, A. and Costantino U. (1996) Layered Metal Phosphates and Their Intercalation Chemistry, in Comprehensive Supramolecular Chemistry (eds G. Alberti and T. Bein) Pergamon Elsevier Ltd Press, Vol. 7, pp. 107. 

Intercalation in layered solids is a long-established phenomenon. It has been suggested [ 1 ] that the first example, dating from over two thousand years ago, involved intercalation in kaolinite (an aluminosilicate clay) and explains the secret behind the production of fine Chinese porcelain, hi modern times, many thousands of papers have been devoted to intercalation chemistry in clays, graphite and other materials. 

Tennakoon DTB, Thomas JM, Tricker MJ, et al. 1974. Smface and intercalate chemistry of layered silicates. Part 1. General introduction and uptake of benzidine and related organic molecrtles by montmorillonite. J Chem Soc Dalton Trans 20 2207-2211. 

Rosseinsky MJ (1995) Fullerene intercalation chemistry. J Mater Chem 5 1497-1513... 

We shall be discussing other types of inclusion compounds formed by layered graphite and Ta 2 as well as other varieties of hosts in Chapter 8, which deals with intercalation chemistry. 

Layered chalcogenides such as TaS2 can accommodate large molecules such as stearamide. We shall be discussing the intercalation chemistry of these and other layered materials in Chapter 8. TaS2 is metallic and superconducting [T = 0.8 K) and the superconducting transition is increased to 3.5 K by incorporation of pyridine the interlayer separation increases from 3 to 6 A. Octadecylamine increases the interlayer... 

The brief overview of intercalation chemistry presented above shows that the subject encompasses a fascinating variety of solid state reactions between two- or three-dimensional host materials and guest atoms and molecules. Not all host material that... 

---