Graphite, intercalation compounds with alkali metals

Like the alkali metals, some halogens, particularly fluorine, form intercalated compounds with graphite crystals. Reaction usually starts at 600°C. However, graphite does not react with chlorine at temperatures below that of the electric arc. 

The reaction of various carbonaceous materials with steam to yield CO, CO2, and H2 has been intensively studied. Of special interest has been the catalysis of this reaction by various alkali metal containing compounds, most notably potassium carbonate (32-37). Various mechanisms have been proposed, some including alkali metal atoms (37) or even graphite intercalation compounds (38) as intermediates. 

Nanospaces formed in graphite intercalation compounds with stage-2 structure of alkali metals and gases adsorbed at low temperatures of 196-63 K. Reprinted ftom Ref. [68] with permission from Carbon Society of Japan. 

Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

Figure 8.16 Layer-plane sequence along the c-axis for graphite in various stage I -5 of alkali-metal graphite intercalation compounds. Comparison with Fig. 8.15 shows that the horizontal planes are being viewed diagonally across the figure. /,. is the interlayer repeat distance along the c-axis.

First reported by Fredenhagen in 1926 F3, F4), the graphite-alkali-metal compounds possess a relative simplicity with respect to other intercalation compounds. To the physicist, their uncomplicated structure and well defined stoichiometry permit reasonable band-structure calculations to be made S2,12) to the chemist, their identity as solid, "infinite radical-anions frequently allows their useful chemical substitution for such homogeneous, molecular-basis reductants as alkali metal-amines and aromatic radical anions N2, B5). 

GICs have been first discovered from the reaction of graphite with sulfuric acid more than 150 years ago.30 In the long history of GICs research, a huge number of compounds have been yielded with a large variety of donors and acceptors, in which alkali metals, alkaline earth metals, transition metal chlorides, acids, and halogens are involved as typical intercalates. 

Alkali metals and bromine react with graphite to form solids known as intercalation compounds, where the foreign atoms are inserted between the intact graphite layers. Many other layered solids, for example dichalcogenides such as TaS2, which have structures similar to Cdl2 will also for intercalation compounds. The inserted species may be alkali metals, or electron donor molecules such as amines or organometallic compounds. 

The presence of the potassium atoms causes the distance between the layers of carbon atoms to increase from the value of 235 pm in graphite to 540 pm in C8K. When rubidium and cesium atoms are placed between the layers, the distances between the carbon layers are 561 and 595 pm, respectively. As would be expected for materials that contain atoms of an alkali metal, these materials are extremely reactive in air, and they react explosively with water. A large number of other intercalation compounds have been prepared that have halogens, interhalogens, or metal halides as the included substances. 

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