Chemistry of carbon nanotubes

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The chemistry of carbon nanotubes ( English carbon nanotube chemistry ) deals with chemical reactions that are used to change the properties of carbon nanotubes (CNTs). CNTs can be functionalized in such a way that they have the desired properties for a wide range of applications.

Multi-walled nanotube animation

Two important methods are the functionalization of covalent and non-covalent bonds.

Because of their hydrophobic properties, CNTs tend to clump together, which prevents dispersion in solvents or in viscous polymer melts. The resulting nanotube bundles or coils make the final material less useful. The surface of the CNTs can now be varied in such a way that they are less hydrophobic and that the surface adhesion to a polymer is improved by attaching functional groups . Scheme of nanotube chemistry

Toxicity of the functionalized CNTs

It can be assumed that functionalized CNTs are cytotoxic.

Covalent modification

Covalent modification of nanotubes.

In covalent modification, a functional group is attached to a nanotube. A functional group can be attached either to the side wall or to the end of a nanotube. The ends of the nanotube have the greatest reactivity because of their larger pyramidalization angle, and the side walls of the carbon nanotube have a smaller pyramidalization angle, which has a lower reactivity. Although covalent modifications are very stable, the sp 2 hybridization of the carbon atom to which one is attached is broken because a new σ-bond is formed. The dissolution of the delocalized π-electron system typically reduces the conductivity of the carbon nanotube.

oxidation

The purification and oxidation of CNTs has often been mentioned in the literature. These processes were important for a low-yield representation of carbon nanotubes, where carbon particles and amorphous carbon make up a significant proportion of the material and are still important in attaching functional groups to the surface. During the oxidation, the carbon-carbon bond network of the graphite layers is broken by allowing the introduction of oxygen units, thus forming carboxyl, phenol and lactone groups, which have been sufficiently explored for further chemical functionalization.

Initial investigations into the oxidation of nanotubes used a gas phase reaction with nitric acid vapor, whereby the nanotubes were unselectively functionalized with carboxyl, carbonyl and hydroxyl groups. In liquid phase reactions, nanotubes were treated with the oxidizing solutions nitric acid or aqua regia with the same effect. However, "over-oxidation" can cause the nanotube to break apart into fragments known as carbon fragments. Xing et al. investigated ultrasound-assisted oxidation of CNTs with sulfuric and nitric acid and produced carbonyl and carboxyl groups. If the oxidation with acid is stopped by treatment with hydrogen peroxide, the destruction of the CNT is prevented. Single-walled nanotubes can be shortened with oleum (100% H 2 SO 4 with 3% SO 3 ) and nitric acid.

In one type of reaction, it is oxidized with aniline to the diazonium salt and flushed with nitrogen, so that a covalent bond is formed in which an aryl radical is formed. The oxidation reagent is isoamyl nitrite in an aqueous suspension.

On Water Nanotube Functionalization

Esterification / amide formation

Carboxylic acids are the precursors for esterification and amide formation. The carboxyl group is first converted to the acid chloride with thionyl chloride or with oxalyl chloride, which is then converted to the amide, amine or alcohol. CNTs can be coated with silver nano-particles using amination reactions. Amide-functionalized CNTs were presented as chelates for silver nanoparticles. CNTs modified with acyl chloride react with branched molecules such as polyamidoamine, which can be used as a template for silver ions and is later reduced with formamide . Amino-modified CNTs can be prepared by reacting an acyl chloride-modified CNT with ethylenediamine .

Cycloaddition

There are cycloaddition reactions such as Diels-Alder reactions or 1,3-dipolar cycloaddition with azomethine ylidene known, as azide-alkyne cycloaddition. An example is a Diels-Alder reaction with chromium hexacarbonyl under high pressure. The I D / I G isomer ratio in the reaction with Danishefsky ’s diene is 2.6.

The best-known 1,3-cycloaddition is the reaction of a CNT with an azomethine ylide. The addition of pyrrolidine can lead to a number of functional groups, such as polyamidoamine dendrimers , phthalocyanines, perfluoroalkylsilanes, and aminoethylene glycol groups. The Diels – Alder cycloaddition occurs primarily with fluorinated CNTs. As is known, starting materials for Diels-Alder reactions are dienes such as 2,3-dimethyl-1,3-butadienes, anthracenes and 2-trimethylsiloxyl-1,3-butadienes.

Radical addition

Electron microscope image of CNTs with (a) the 4- (1-pyrenyl) phenyl radical and (b) its boric acid ester, below: the corresponding models.

The modification of CNTs with aryldiazonium salts was first described by Tour et al. examined. Because of the extreme reaction conditions for the in situ generation of the diazonium ion, other methods were sought. Stephenson et al. report a reaction of aniline derivatives with sodium nitride in 96% sulfuric acid and ammonium persulfate. Price et al. conducted the reaction under milder reaction conditions by stirring CNTs in water and treating them with aniline and mild oxidizing agent. Diazonium chemistry has been used to make further modifications to CNTs such as: B. with the Suzuki reaction and the Heck reaction . Coupling reactions were performed with iodophenyl-functionalized CNTs. Wong et al. showed silylation reactions with trimethoxysilane and with heptaphenyldisilane under mild photochemical reaction conditions.

Nucleophilic addition

Hirsch et al. performed nucleophilic additions with organolithium reagents and with organomagnesium compounds to CNTs. After subsequent air oxidation, they were able to produce alkyl-modified CNTs. Hirsch was able to demonstrate nucleophilic addition with amines by generating lithium amides, which led to amino-modified CNTs.

Electrophilic addition

Nanotubes can also be alkylated with alkyl halides using lithium or sodium and liquid ammonia, as in a Birch reduction . Nanotube salts can act as a polymerization initiator and can react with peroxides to form alkoxy-functionalized nanotubes.

The alkyl and hydroxy modification of CNTs was performed by the electrophilic addition of alkyl halides under microwave irradiation. Tessonier et al. modified CNTs by deprotonation with butyllithium and subsequent amino substitution. Balaban et al. performed Friedel-Crafts alkylations with nitrobenzene at 180 ° C with aluminum chloride on CNTs.

Non-covalent modifications

Non-covalent modification of carbon nanotubes.

Non-covalent modifications use van der Waals forces and π-π interactions through adsorption of polycondensed aromatics, surfactants , polymers and biomolecules. Non-covalent modifications do not destroy the configuration of the CNT at the expense of chemical stability and are advantageous for phase separations and dissociations of solids between two phases.

Condensed aromatic compounds

Condensed aromatics, which have hydrophilic and hydrophobic units, are used to dissolve CNTs in organic or aqueous solutions. Some of these amphiphiles are phenyl , naphthyl, phenanthryl, pyrene , and porphyrin systems. The greater the π-π interaction of the aromatic amphiphiles, the better the solubility. These aromatic systems can be varied with amino and carboxyl groups to functionalize the CNTs.

Biomolecules

The interactions between CNTs and biomolecules have been extensively studied because of their potential for biological applications. Modifications of CNTs have been visualized with proteins, carbohydrates and nucleic acids using the bottom-up technique . Proteins have a high affinity for CNTs because the amino acids they are made up of can be both hydophilic and hydophobic. Polysaccharides have been used successfully to modify CNTs to form stable hybrids. To make CNTS water soluble, phospholipids such as lysoglycerophosopholipids have been used.

π-π interaction and electrostatic interactions

Bifunctional molecules are used to modify CNTs. One end of the molecule is a polyaromatic component that enters into π-π interactions with the nanotube . The other end of the same molecule has a functional group such as amino, carboxy or thiol groups. For example, pyrene derivatives and aryl thiols have been used as substrates for various metal nanobeads such as gold, silver and platinum.

characterization

A useful analytical method for CNTs is Raman spectroscopy . There is a G-band at 1580 cm −1 and a D-band at 1350 cm −1 . The ratio of the two peaks indicates the degree of functionalization.

literature

  • Klaus Müllen , Xinliang Feng (Ed.): Chemistry of Carbon-Nanostructures , De Gruyter 2017

Individual evidence

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