Diamond-graphite hybrids

Block-copolymeis of graphite and diamond (diamond-graphite hybrids)... 

Carbon nanotubes (CNTs) constitute a nanostructured carbon material that consists of rolled up layers of sp2 hybridized carbon atoms forming a honeycomb lattice. After diamond, graphite and fullerenes, the one-dimensional tubular structure of CNTs is considered the 4th allotrope of carbon (graphene is the 5th). 

In this chapter, the structures and textures of carbons at different scales are explained. The carbon materials are classified into four families, diamond, graphite, fullerene, and carbyne on the basis of hybridized sp3, flat sp2, curved sp2, and sp orbitals used, respectively. Each family has its own characteristic diversity in structure and also in the possibility of accepting foreign species. The formation of these carbon materials from organic precursors (carbonization) is shortly described by dividing the process into three phases (gas, solid, and liquid), based on the intermediate phases formed during carbonization. The importance of nanotexture, mainly due to the preferred orientation of the anisotropic BSU in the graphite family, i.e., planar, axial, point, and random orientation schemes, is particularly emphasized. 

Many forms of carbon materials do exist with a continuous variation in the structure/nanotexture and properties between the graphite (sp2 hybrid orbitals) and diamond (sp3 hybrid orbitals) limiting structures. 

Carbon occurs in the allotropes (different forms) diamond, graphite, and the fullerenes. The fullerenes are molecular solids (see Section 16.6), but diamond and graphite are typically network solids. In diamond, the hardest naturally occurring substance, each carbon atom is surrounded by a tetrahedral arrangement of other carbon atoms, as shown in Fig. 16.26(a). This structure is stabilized by covalent bonds, which, in terms of the localized electron model, are formed by the overlap of sp3 hybridized atomic orbitals on each carbon atom. 

The structure of F2, CI2, O2. the sulfur chain, Nj, P4, diamond, graphite. Resonance hybrid structures. 

Carbon, a versatile element, can have many allotropic forms. The two pure forms known for centuries are diamond (sp hybridization) and graphite (sp hybridization). A linear carbon chain (one-dimensional)... 

Carbon nanotubes can thus be visualized as a sheet of graphite that has been rolled into a tube. Unlike the diamond (sp hybridization), where the 3D diamond cubic crystal stmcture is formed with each carbon atom having four... 

Compare the hybridization and structure of carbon in diamond and graphite. How do these features explain the physical properties of the two allotropes ... 

In diamond, carbon is sp hybridized and forms a tetrahedral, three-dimensional network structure, which is extremely rigid. Graphite carbon is sp2 hybridized and planar. Its application as a lubricant results from the fact that the two-dimensional sheets can slide across one another, thereby reducing friction. In graphite, the unhybridized p-electrons are free to move from one carbon atom to another, which results in its high electrical conductivity. In diamond, all electrons are localized in sp3 hybridized C—C cr-bonds, so diamond is a poor conductor of electricity. 

It is well known that the stable crystalline form of carbon at ambient conditions is graphite, which is fully sp hybidized. The synthesis of the fully sp -hybridized crystalline diamond is performed at high temperatures and pressures. So, the production of metastable carbon solids with a high fraction of sp -hybridized... 

The same principles that are valid for the surface of crystalline substances hold for the surface of amorphous solids. Crystals can be of the purely ionic type, e.g., NaF, or of the purely covalent type, e.g., diamond. Most substances, however, are somewhere in between these extremes [even in lithium fluoride, a slight tendency towards bond formation between cations and anions has been shown by precise determinations of the electron density distribution (/)]. Mostly, amorphous solids are found with predominantly covalent bonds. As with liquids, there is usually some close-range ordering of the atoms similar to the ordering in the corresponding crystalline structures. Obviously, this is caused by the tendency of the atoms to retain their normal electron configuration, such as the sp hybridization of silicon in silica. Here, too, transitions from crystalline to amorphous do occur. The microcrystalline forms of carbon which are structurally descended from graphite are an example. 

Carbon exists in more than 40 known structural forms, or allotropes, several of which are crystalline but most of which are amorphous. Graphite, the most common allotrope of carbon and the most stable under normal conditions, is a crystalline covalent network solid that consists of two-dimensional sheets of fused six-membered rings (Figure 10.26a). Each carbon atom is sp2-hybridized and is connected to three other carbons. The diamond form of elemental carbon is a covalent network solid in which each carbon atom is sp3-hybridized and is bonded with tetrahedral geometry to four other carbons (Figure 10.26b). 

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