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Carbon Nanotubes 101 – Purification Methods
Purification of CNTs generally refers to the separation of CNTs from other entities, such as carbon nanoparticles, amorphous carbon, residual catalyst, and other unwanted species. The classic chemical techniques for purification have been tried, but they have not been found to be effective in removing the undesirable impurities. Three basic methods have been used with varying degrees of success, namely gas-phase, liquid-phase, and intercalation methods.
Generally, a centrifugal separation is necessary to concentrate the single walled nanotubes in low-yield soot before the micro filtration operation, since the nanoparticles easily contaminate membrane filters. The advantage of this method is that unwanted nanoparticles and amorphous carbon are removed simultaneously and the CNTs are not chemically modified. However 2-3 mol nitric acid is useful for chemically removing impurities.
It is now possible to cut CNTs into smaller segments, by extended sonication in concentrated acid mixtures. The resulting CNTs form a colloidal suspension in solvents. They can be deposited on substrates, or further manipulated in solution, and can have many different functional groups attached to the ends and sides of the CNTs.
The first successful technique for purification of nanotubes was developed by Thomas Ebbesen and coworkers. Following the demonstration that nanotubes could be selectively attached by oxidizing gases these workers realized that nanoparticles, with their defect rich structures might be oxidised more readily than the relatively perfect nanotubes. They found that a significant relative enrichment of nanotubes could be achieved this way, but only at the expense of losing the majority of the original sample.
A new gas-phase method has been developed at the NASA Glenn Research Center to purify gram-scale quantities of single-wall CNTs. This
method, a modification of a gas-phase purification technique previously reported by Smalley and others, uses a combination of high-temperature oxidations and repeated extractions with nitric and hydrochloric acid. This improved procedure significantly reduces the amount of impurities such as residual catalyst, and non-nanotube forms of carbon) within the CNTs, increasing their stability significantly.
The current liquid-phase purification procedure follows certain essential steps:
– preliminary filtration- to get rid of large graphite particles;
– dissolution- to remove fullerenes (in organic solvents) and catalyst particles (in concentrated acids)
– centrifugal separation-
– microfiltration- and
It is important to keep the CNTs well-separated in solution, so the CNTs are typically dispersed using a surfactant prior to the last stage of separation.
An alternative approach to purifying multi walled nanotubes was introduced in 1994 by a Japanese research group. This technique made use of the fact that nanoparticles and other graphitic contaminants have relatively “open” structures and can therefore be more readily intercalated with a variety of materials that can close nanotubes.
By intercalating with copper chloride, and then reducing this to metallic copper, the research group was able to preferentially oxidize the nanoparticles away, using copper as an oxidation catalyst. Since 1994, this has become a popular method for purification of nanotubes.
The first stage is to immerse the crude cathodic deposit in a molten copper chloride and potassium chloride mixture at 400°C and leave it for one week. The product of this treatment, which contains intercalated nanoparticles and graphitic fragments, is then washed in ion exchanged water to remove excess copper chloride and potassium chloride. In order to reduce the intercalated copper chloride-potassium chloride metal, the washed product is slowly heated to 500°C in a mixture of Helium and hydrogen and held at this temperature for 1 hour.
Finally, the material is oxidized in flowing air at a rate of 10°C/min to a temperature of 555°C. Samples of cathodic soot which have been treated this way consist almost entirely of nanotubes. A disadvantage of this method is that some amount of nanotubes are inevitably lost in the oxidation stage, and the final material may be contaminated with residues of intercalates. A similar purification technique, which involves intercalation with bromine followed by oxidation, has also been described.