2.1 Carbon nanomaterials  (Page 4/9)

Cycloaddition is another powerful tool to functionalize fullerenes, in particular because of its selectivity with the 6,6 bonds, limiting the possible isomers ( [link] ). The dienophilic feature of the [6,6] double bonds of C ₆₀ enables the molecule to undergo various cycloaddition reactions in which the monoadducts can be generated in high yields. The best studies cycloadditon reactions of fullerene are [3+2] additions with diazoderivatives and azomethine ylides (Prato reactions). In this reaction, azomethine ylides can be generated in situ from condensation of α-amino acids with aldehydes or ketones, which produce 1,3 dipoles to further react with C ₆₀ in good yields ( [link] ). Hundreds of useful building blocks have been generated by those two methods. The Prato reactions have also been successfully applied to carbon nanotubes.

The oxidation of fullerenes, such as C ₆₀ , has been of increasing interest with regard to applications in photoelectric devices, biological systems, and possible remediation of fullerenes. The oxidation of C ₆₀ to C ₆₀ O _n (n = 1, 2) may be accomplished by photooxidation, ozonolysis, and epoxidation. With each of these methods, there is a limit to the isolable oxygenated product, C ₆₀ O _n with n<3. Highly oxygenated fullerenes, C ₆₀ O _n with 3 ≤ n ≤ 9, have been prepared by the catalytic oxidation of C ₆₀ with ReMeO ₃ /H ₂ O ₂ .

Carbon nanotubes

A key breakthrough in carbon nanochemistry came in 1993 with the report of needle-like tubes made exclusively of carbon. This material became known as carbon nanotubes (CNTs). There are several types of nanotubes. The first discovery was of multi walled tubes (MWNTs) resembling many pipes nested within each other. Shortly after MWNTs were discovered single walled nanotubes (SWNTs) were observed. Single walled tubes resemble a single pipe that is potentially capped at each end. The properties of single walled and multi walled tubes are generally the same, although single walled tubes are believed to have superior mechanical strength and thermal and electrical conductivity; it is also more difficult to manufacture them.

Single walled carbon nanotubes (SWNTs) are by definition fullerene materials. Their structure consists of a graphene sheet rolled into a tube and capped by half a fullerene ( [link] ). The carbon atoms in a SWNT, like those in a fullerene, are sp2 hybridized. The structure of a nanotube is analogous to taking this graphene sheet and rolling it into a seamless cylinder. The different types of SWNTs are defined by their diameter and chirality. Most of the presently used single-wall carbon nanotubes have been synthesized by the pulsed laser vaporization method, however, increasingly SWNTs are prepared by vapor liquid solid catalyzed growth.