Polymer-functionalized multiwalled carbon nanotubes as lithium intercalation hosts

Multiwalled carbon nanotubes (MWNTs) functionalized with a hyperbranched aliphatic polyester and two different poly(ethylene glycol)s were synthesized by the reactions of carbonyl chloride groups on the surface of MWNTs and hydroxyl groups of polymers. Electrochemical intercalation of lithium in the three materials was investigated with galvanostatic charge-discharge experiments. The hyperbranched polymer-functionalized MWNT as an electrode material for lithium batteries showed a significant improvement over linear polymer-functionalized MWNTs in lithium insertion/deinsertion capacity and cycle stability. The MWNT functionalized with linear poly(ethylene glycol) showed a high initial capacity of lithium insertion/deinsertion but had the highest capacity fade rate among the materials. Because the polymers were chemically localized in the electrode-electrolyte interface, the comparison between hyperbranched and linear polymer-modified MWNTs manifested the important influence of the electrode-electrolyte interface on the electrochemical properties of lithium batteries.     

Modifications of carbon nanotubes with polymers

The chemical functionalizations of carbon nanotubes (CNTs) could enhance their chemical compatibility and dissolution properties, which enable both a more extensive characterization and subsequent chemical reactivity. The modifications with polymers could not only improve CNTs’ solubility and dispersibility but also the interfacial interaction to polymeric matrices in its composites. The main methods for the modification of CNTs with polymers are noncovalent attachment (polymer wrapping and absorption) and covalent attachment (“grafting to”and “grafting from”). The current states of the literatures in the field are presented in this review.     

Selective oxidation of metallic single-walled carbon nanotubes

In this work we present a simple and non-invasive approach to the preparation of semi-conducting single-walled carbon nanotubes (SWCNTs) through selective destruction of the metallic counterparts present in the starting material. Most separation techniques require chemical treatment, the application of ultrasound, or the addition of auxiliary molecules, which lead to the introduction of defects and impurities. In this contribution, laser ablation SWCNTs were selectively oxidised via long-term heating leading to the enrichment of semi-conductive nanotubes. Spectroscopic analysis demonstrates that the selective character of oxidation occurs only in the optimal temperature range, determined by thermo-gravimetric analysis. By tuning the process parameters, one can obtain a sample exhibiting different purity (up to 95 % of semi-conducting nanotubes) and separation efficiency. The samples’ quality and yield of separation were determined by UV-VIS-NIR spectroscopy, Raman spectroscopy, and TG analysis. The approach presented is readily scaleable.     

Electronic conduction in polymers, carbon nanotubes and graphene

In the years since the discovery of organic polymers that exhibited electrical conductivities comparable to some metals, other novel carbon-based conductors have been developed, including carbon nanotubes and graphene (monolayers of carbon atoms). In this critical review, we discuss the common features and the differences in the conduction mechanisms observed in these carbon-based materials, which range from near ballistic and conventional metallic conduction to fluctuation-assisted tunnelling, variable-range hopping and more exotic mechanisms. For each category of material, we discuss the dependence of conduction on the morphology of the sample. The presence of heterogeneous disorder is often particularly important in determining the overall behaviour, and can lead to surprisingly similar conduction behaviour in polymers, carbon nanotube networks and chemically-derived graphene (122 references).     

Selective placement of carbon nanotubes on metal-oxide surfaces

We describe a method to selectively position carbon nanotubes on Al2O3 and HfO2 surfaces. The method exploits the selective binding of alkylphosphonic acids to oxide surfaces with large isoelectric points (i.e. basic rather than acidic surfaces). We have patterned oxide surfaces with acids using both microcontact printing and conventional lithography. With proper choice of the functional end group (e.g., -CH3 or -NH2), nanotube adhesion to the surface can be either prevented or enhanced.     

Selective dispersion of single-walled carbon nanotubes in the presence of polymers: the role of molecular and colloidal length scales

Dimensionality is known to play a key role in the solution behavior of nano- and mesoparticles. In particular, the shape and the range of the attractive van der Waals interparticle potential are determined by the number of microscopic versus mesoscopic dimensions. For single-walled nanotubes (SWNTs), where two of the dimensions are nanoscopic and one is mesoscopic, the intertube attraction is relatively short ranged, albeit very steep. The very large attraction (compared to the thermal energy, K(b)T) among long SWNTs leads to aggregation at different levels and constitutes a major barrier for manipulation and utilization of SWNTs. This study demonstrates that it is possible to shape the intertube potential by decorating SWNTs with end-tethered polymers. In good solvent conditions for the polymers, entropic repulsion among the tethered chains generates a free energy barrier that prevents SWNTs from approaching the attractive part of the intertube potential. Consequentially, stable dispersions of individual, well separated SWNTs can be prepared. Investigation of different chain lengths and tethering densities of the polymers as well as the interparticle potentials for nanometric versus mesoscopic particles suggests that polymer-induced steric stabilization provides a generic method for separation of SWNTs from mixtures of colloidal species, as demonstrated experimentally.     

Selective interactions of porphyrins with semiconducting single-walled carbon nanotubes

A derivatized porphyrin with long alkyl chains, 5,10,15,20-tetrakis(hexadecyloxyphenyl)-21H,23H-porphine, is selective toward semiconducting single-walled carbon nanotubes (SWNTs) in presumably noncovalent interactions, resulting in significantly enriched semiconducting SWNTs in the solubilized sample and predominantly metallic SWNTs in the residual solid sample according to Raman, near-IR absorption, and bulk conductivity characterizations.     

Debundling of multiwalled carbon nanotubes in N,N-dimethylacetamide by polymers

Structure and properties of the dispersions of multiwalled carbon nanotubes (MWCNTs) in N,N-dimethylacetamide (DMAc) with different dispersing polymers: polyvinylpyrrolidone (PVP), poly(ethyleneoxide), triblock copolymers poly(ethyleneoxide)-b-poly(propyleneoxide)-b-poly(ethyleneoxide) (Pluronic F127 and Pluronic F108), ethylenediamine tetrakis(ethoxylate-b-propoxylate) tetrol, and ethylenediamine tetrakis(propoxylate-b-ethoxylate) tetrol (Tetronic) of different molecular weights were studied. All studied polymers were shown to be able to disperse MWCNT in DMAc, and MWCNT dispersions appear free of aggregates by visual inspection even after 3 months of keeping at room temperature. Dispersions were characterized by UV–VIS absorption spectroscopy and dynamic light scattering measurements. PVP was found to be the best dispersing polymer for MWCNT in DMAc. It was shown that the yield of the dispersed MWCNT and the average particle size of the MWCNT in DMAc depend on the chemical nature, molecular weight of the dispersing polymer, and solvent quality. The difference in dispersive capacity of the studied polymers is attributed to different dispersion mechanisms for PVP (“polymer wrapping” model) and for other studied dispersing polymers (“loose adsorption” model), which have different efficiencies in DMAc. It was revealed that an increase of dispersing polymer (PVP) concentration at the range of 4.7–37.6 g l^?1 results in an average particle size enlargement and MWCNT final concentration reduction.     

Noncovalent functionalization of multi-walled carbon nanotubes by pyrene containing polymers

Multi-walled carbon nanotubes (MWNTs) have been solubilized in water and in various organic solvents by noncovalent side-wall functionalization by pyrene containing polymers.     

Selective oxidation on metallic carbon nanotubes by halogen oxoanions

Chlorine oxoanions with the chlorine atom at different oxidation states were introduced in an attempt to systematically tailor the electronic structures of single-walled carbon nanotubes (SWCNTs). The degree of selective oxidation was controlled systematically by the different oxidation state of the chlorine oxoanion. Selective suppression of the metallic SWCNTs with a minimal effect on the semiconducting SWCNTs was observed at a high oxidation state. The adsorption behavior and charge transfer at a low oxidation state were in contrast to that observed at a high oxidation state. Density functional calculations demonstrated the chemisorption of chloro oxoanions at the low oxidation state and their physisorption at high oxidation states. These results concurred with the experimental observations from X-ray photoelectron spectroscopy. The sheet resistance of the SWCNT film decreased significantly at high oxidation states, which was explained in terms of a p-doping phenomenon that is controlled by the oxidation state.     

Selective photochemical functionalization of surfactant-dispersed single wall carbon nanotubes in water

Ultraviolet (UV) irradiation of single wall carbon nanotubes (SWCNTs) individually dispersed in surfactants leads to diameter and type-selective photohydroxylation of the nanotubes. Photohydroxylation of first semiconductor and then small diameter metallic SWCNTs was confirmed after 254 nm UV irradiation in acidic, neutral, and basic aqueous solutions at ambient and elevated temperatures. The increased oxygen content of the SWCNTs after UV irradiation, as detected by X-ray photoelectron spectroscopy, suggests that SWCNTs were hydroxylated by reaction with water. Attenuated total reflectance Fourier transform infrared analysis provides evidence of hydroxyl functional groups on their surface. This photochemical reaction is impeded by molecular oxygen and appears to involve a reactive intermediate generated in the vicinity of semiconducting SWCNTs. This represents a noncontaminating selective reaction in the liquid phase that uses an intrinsic property of the tubes.     

The increasing importance of carbon nanotubes and nanostructured conducting polymers in biosensors

The growing need for analytical devices requiring smaller sample volumes, decreased power consumption and improved performance have been driving forces behind the rapid growth in nanomaterials research. Due to their dimensions, nanostructured materials display unique properties not traditionally observed in bulk materials. Characteristics such as increased surface area along with enhanced electrical/optical properties make them suitable for numerous applications such as nanoelectronics, photovoltaics and chemical/biological sensing. In this review we examine the potential that exists to use nanostructured materials for biosensor devices. By incorporating nanomaterials, it is possible to achieve enhanced sensitivity, improved response time and smaller size. Here we report some of the success that has been achieved in this area. Many nanoparticle and nanofibre geometries are particularly relevant, but in this paper we specifically focus on organic nanostructures, reviewing conducting polymer nanostructures and carbon nanotubes.     

Selective host-guest interaction of single-walled carbon nanotubes with functionalised fullerenes

Exohedrally functionalised fullerenes have been inserted in single-walled carbon nanotubes (SWNTs) with the aid of supercritical carbon dioxide to form peapods; C(61)(COOEt)(2) are encapsulated in SWNTs in high yield, whereas C(61)(COOH)(2) aggregate via hydrogen bonding to form a supramolecular complex, which sterically hinders encapsulation and causes it to adhere to the exterior surface of the SWNTs.     

Selective oxidation of semiconducting single-wall carbon nanotubes by hydrogen peroxide

Selective oxidation of single-wall carbon nanotubes (SWCNTs) by H2O2 was conducted at varying heating times and monitored by UV-vis-NIR spectroscopy. A major increase in the relative absorption intensity indicated a higher than 80% concentration of metallic SWCNTs in the final product. Here, it is suggested that semiconducting SWCNTs are more reactive than metallic SWCNTs because of hole-doping by H2O2, resulting in faster oxidation.     

Combining single wall carbon nanotubes and photoactive polymers for photoconversion

A combination of van der Waals and electrostatic interactions was used to integrate SWNT and a suitably functionalized polythiophene into nanostructured ITO electrodes. In the resulting electron donor/acceptor nanocomposites, polythiophene represents the light-harvesting chromophore that readily donates an excited-state electron to the ground-state electron-accepting SWNT. Upon illumination, monochromatic incident photoconversion efficiencies between 1.2 and 9.3% were determined for single and eight-sandwiched layers, respectively.     

Modification of epoxy polymers with small additives of multiwall carbon nanotubes

The effect of small additives of functionalized multiwall carbon nanotubes used as a modifier on the formation and properties of epoxy polymers cured with diaminodiphenyl sulfone is investigated. In the range of additive concentrations 0.01–0.50 wt %, there are extreme dependences of dynamic storage modulus and the glass-transition temperature on modifier concentration. As shown by electron microscopy and X-ray scattering, regions with increased packing densities of macromolecules are formed in the polymers in the presence of the modifier. The effect of the specific surface on the kinetics of curing of epoxy resins is observed. A mechanism controlling the formation of the epoxy matrix that is responsible for the inhomogeneous polymer structuring that defines the final properties of the polymers is suggested.