MWCNTs groups

As for the coherent length in CNTs, a very interesting paper has been published from the group at the Georgia Institute of Technology about the conductance of individual MWCNTs [34], They have observed the quantisation of conductance by changing the distance between the two electrodes. This result indicates ballistic conduction in a CNT, which suggests the formation of stationary waves of electrons inside CNTs. 

The group in the Swiss Federal Institute of Technology [55] has fabricated a macroscale device by depositing the conducting polymer (poly(/j-phenylenevinylene)) on the MWCNT film (Fig. 16). They have observed the characteristic rectifying effect from the l-V curve, which suggests the CNTs inject holes efficiently into the polymer layer. However, due to the difficulty in... 

The majority of studies have used surfactants that wrap around nanocarbons via van der Waals interactions [37]. For instance, surfactants such as sodium dodecylsulfate (SDS) are commonly used to disperse CNTs in aqueous solutions [38,39] while other surfactants, such as Pluorinc-123, are used to mechanically exfoliate graphene from graphite flakes (Fig. 5.4(a)) [40,41]. The polar head group of the surfactant can be used to further hybridize the nanocarbon via a range of covalent or noncovalent interactions [42]. For example, nanoparticles of Pt [43,44] and Pd [45] have been decorated onto SDS-wrapped MWCNTs. Similarly, Whitsitt et al. evaluated various surfactants for their ability to facilitate the deposition of Si02 NPs onto SWCNTs [46,47]. As an exam-... 

It is thus evident that the characteristics of nanocarbons (conductivity, local structure, presence of defects and functional groups, morphology, etc.) are critical to determining the properties of the hybrid nanomaterial with the semiconductor. However, most of the literature studies put emphasis on the analysis of semiconductor characteristics, while often nanocarbons are only described in generic terms (CNT, for example). Yet, it is well known how the properties of nanocarbons can be considerably different from case to case (depending on details in preparation), even if the structure is formally the same (MWCNT, for example). 

Defects in MWCNTs are always present. We can briefly differentiate between topological defects which lead to rehybridization (C5 and C7 rings instead of C6 lead to rehybridization between sp2 and sp3) and incomplete bonding defects (vacancies, dislocation) (Fig. 16.2). Functionalization or doping with heteroelements may add further modifications with respect to the ideal ordered structure, but are also the sites which allow for anchoring supported metals or metal oxides, or to functionalize the CNTs with organic groups. 

Among the surface-modified CNTs materials, a bulk-modified CNT paste (CNTP) has also been reported [126]. The new composite electrode combined the ability of CNTs to promote adsorption and electron-transfer reactions with the attractive properties of the composite materials. The CNTP was prepared by mixing MWCNTs powder (diameter 20-50 nm, length 1-5 jim) and mineral oil in a 60 30 ratio. The oxidation pretreatment [performed in ABS (pH 5.0) for 20 s at 1.30 V, vs Ag/AgCl] proved to be critical in the state of the CNTP surface. Pretreatments improved the adsorption and electrooxidation of both DNA and DNA bases, probably due to the increase in the density of oxygenated groups. 

Ferrocene was one of the earliest mediators used [10] but is somewhat hydrophobic so derivatives of the molecule are often employed [39-43]. Ferricyanide can also be used, and the use of MWCNT with this mediator was shown to enhance its effectiveness [33]. Other groups have studied a wide diversity of novel mediator systems such as poly(vinylferrocene-co-acrylamide) dispersed within an alumina nanoparticle membrane [34], ruthenium [35] and osmium [36,37] complexes, and the phenazine pigment pyocyanin, which is produced by the bacteria Pseudomonas aeruginosa [38]. 

The reaction between toluene 2,4-diisocyanate and carboxylated MWCNTs afforded amido-functionalized nanotubes containing highly reactive isocyanate groups on their surface (Scheme 1.4). The amount of the isocyanate groups was determined by chemical titration and thermogravimetric analysis (TGA) [105]. The modified tubes may constitute promising components to prepare polymer-nanotube composites and coatings [106]. 

Newkome-type dendrons were attached to the carbon scaffold of SWCNTs and MWCNTs by defect group functionalization [108], First- and second-generation amine dendrons such as those depicted in Fig. 1.5 were condensed with the carboxyl groups of purified and opened SWCNTs and MWCNTs according to the car-bodiimide technique [108], These CNTderivatives can be expected to combine the characteristics of carbon nanotubes with those of dendrimers, potential building blocks for supramolecular, self-assembling and interphase systems. 

A novel chemical functionalization method for MWCNTs through an oxidation and silylation process was reported in 2002. Purified and oxidatively functionalized MWCNTs were reacted with 3-mercaptopropyltrimethoxysilane, the CNT surface being joined to the organosilane moieties through OH groups [143], Similarly, MWCNTs were functionalized by KMn04 oxidation under PTC catalysis and subsequent reaction with the hydrolysis product of 3-methacryloxypropyltri-methoxysilane (3-MPTS) (Scheme 1.13). The O-silyl-functionalized MWCNTs were characterized by FT-IR spectroscopy and energy-dispersive spectroscopy... 

EDS), SEM and TEM analysis [70]. The method allowed different organo-func-tional groups to be attached to MWCNTs, improving their compatibility with specific polymers for producing CNT-based composites. 

A fluorinated octyltrichlorosilane was reacted with the carboxylic moieties of oxidized MWCNTs and, after reduction with the corresponding alcohol groups. The modification was confirmed by XPES and TGA [144],... 

Direct proof of sidewall thiolation has been claimed recently [33], based on analyses of elemental maps in high-resolution TEM images. The authors also proposed that such sulfur functionalities replace the carboxyl and phenolic surface groups upon treatment of previously oxidized MWCNT with phosphorus pentasulfide, as follows ... 

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