Rational Chemical Strategies for Carbon Nanotube Functionalization

Abstract

Whereas the chemistry of fullerenes is well‐established, the chemistry of single‐walled carbon nanotubes (SWNTs) is a relatively unexplored field of research. Investigations into the bonding of moieties onto SWNTs are important because they provide fundamental structural insight into how nanoscale interactions occur. Hence, understanding SWNT chemistry becomes critical to rational, predictive manipulation of their properties. Among the strategies discussed include molecular metal complexation with SWNTs to control site‐selective chemistry in these systems. In particular, work has been performed with Vaska's and Wilkinson's complexes to create functionalized adducts. Functionalization should offer a relatively simple means of tube solubilization and bundle exfoliation, and also allows for tubes to be utilized as recoverable catalyst supports. Solubilization of oxidized SWNTs has also been achieved through derivatization by using a functionalized organic crown ether. The resultant adduct yielded concentrations of dissolved nanotubes on the order of 1 g L−1 in water and at elevated concentrations in a range of organic solvents, traditionally poor for SWNT manipulation. To further demonstrate chemical processability of SWNTs, we have subjected them to ozonolysis, followed by treatment with various independent reagents, to rationally generate a higher proportion of oxygenated functional groups on the nanotube surface. This protocol has been found to purify nanotubes. More importantly, the reaction sequence has been found to ozonize the sidewalls of these nanotubes. Finally, SWNTs have also been chemically modified with quantum dots and oxide nanocrystals. A composite heterostructure consisting of nanotubes joined to nanocrystals offers a unique opportunity to obtain desired physical, electronic, and chemical properties by adjusting synthetic conditions to tailor the size and structure of the individual sub‐components, with implications for self‐assembly.