Double-walled carbon nanotubes: challenges and opportunities

Double-walled carbon nanotubes are coaxial nanostructures composed of exactly two single-walled carbon nanotubes, one nested in another. This unique structure offers advantages and opportunities for extending our knowledge and application of the carbon nanomaterials family. This review seeks to comprehensively discuss the synthesis, purification and characterization methods of this novel class of carbon nanomaterials. An emphasis is placed on the double wall physics that contributes to these structures' complex inter-wall coupling of electronic and optical properties. The debate over the inner-tube photoluminescence provides an interesting illustration of the rich photophysics and challenges associated with the myriad combinations of the inner and outerwall chiralities. Outerwall selective covalent chemistry will be discussed as a potential solution to the unattractive tradeoff between solubility and functionality that has limited some applications of single-walled carbon nanotubes. Finally, we will review the many different uses of double-walled carbon nanotubes and provide an overview of several promising research directions in this new and emerging field.     

Density functional study of the metallization of a linear carbon chain inside single wall carbon nanotubes

By means of the density functional theory, we studied the relaxed structure and electronic properties of new one-dimensional carbon nanostructures conformed by a linear carbon chain (LCC) inside (5,5) and (8,0) single-walled carbon nanotubes (SWCNTs). The calculations were performed with a linear combination of atomic orbitals method using pseudopotentials and the generalized gradient approximation for the exchange-correlation potential. We analyzed the atomic structure, band structure, and the local density of states. We found that, despite the fact that LCC and (8,0) SWCNT have a band gap, the system LCC@(8,0) shows a metallic character. This metallic behavior is provided by the electronic states from the LCC exclusively, due to charge transfer from carbon nanotube to the LCC. However, the electronic characters of the nanotubes in LCC@SWCNT are the same as that of isolated SWCNTs.     

Simultaneous synthesis of vertically aligned carbon nanotubes and amorphous carbon thin films on stainless steel

Carbonaceous nanostructures such as carbon nanotubes, graphene and transparent carbon-based thin films are envisioned to be part of the next generation of electronic devices, mechanical structures, and energy-storage systems. To synthesize these nanostructures on a large scale by chemical vapor deposition, large-area, flexible substrates are needed. Here, we studied the role of a metallic foil, stainless steel, as a self-catalytic substrate for carbon nanostructure synthesis. As a result, vertically aligned carbon nanotubes and amorphous carbon thin films were simultaneously obtained. We further showed that the evolution of the stainless steel foil during the different steps of the process played a critical role in carbon nanotubes and carbon thin film growth. A better understanding of how the growth of these carbon nanostructures is affected by stainless steel evolution under chemical vapor deposition conditions will enable the synthesis of hybrid carbon nanotubes/amorphous carbon nanostructures and pave the way to scale-up of their low-cost production.     

Mechanical properties of polygonal carbon nanotubes

A group of polygonal carbon nanotubes (P-CNTs) have been designed and their mechanical behavior was investigated by classical molecular dynamics simulations. The research aimed at exploring the effects of structure, temperature, and strain rate on the mechanical properties. The results indicate that the Young's modulus of P-CNTs is lower than those of circumcircle carbon nanotubes (C-CNT). Moreover, with an increase in the number of sides to the polygons, the Young's modulus increases and is much closer to that of C-CNT. The effects of temperature and strain rate on the mechanical properties of P-CNTs show that the higher temperature and slower strain rate result in a lower critical strain and weaker tensile strength. In addition, it was found that the critical strains of P-CNTs are dependent on the tube size. Finally, we used the transition-state theory model to predict the critical strain of P-CNTs at given experimental conditions. It is expected that this work could provide feasible means to manipulate the mechanical properties of novel P-CNTs and facilitate the mechanical application of nanostructures as potential electronic devices.     

Aggregate nanostructures of organic molecular materials

Conjugated organic molecules are interesting materials because of their structures and their electronic, electrical, magnetic, optical, biological, and chemical properties. However, researchers continue to face great challenges in the construction of well-defined organic compounds that aggregate into larger molecular materials such as nanowires, tubes, rods, particles, walls, films, and other structural arrays. Such nanoscale materials could serve as direct device components. In this Account, we describe our recent progress in the construction of nanostructures formed through the aggregation of organic conjugated molecules and in the investigation of the optical, electrical, and electronic properties that depend on the size or morphology of these nanostructures. We have designed and synthesized functional conjugated organic molecules with structural features that favor assembly into aggregate nanostructures via weak intermolecular interactions. These large-area ordered molecular aggregate nanostructures are based on a variety of simpler structures such as fullerenes, perylenes, anthracenes, porphyrins, polydiacetylenes, and their derivatives. We have developed new methods to construct these larger structures including organic vapor-solid phase reaction, natural growth, association via self-polymerization and self-organization, and a combination of self-assembly and electrochemical growth. These methods are both facile and reliable, allowing us to produce ordered and aligned aggregate nanostructures, such as large-area arrays of nanowires, nanorods, and nanotubes. In addition, we can synthesize nanoscale materials with controlled properties. Large-area ordered aggregate nanostructures exhibit interesting electrical, optical, and optoelectronic properties. We also describe the preparation of large-area aggregate nanostructures of charge transfer (CT) complexes using an organic solid-phase reaction technique. By this process, we can finely control the morphologies and sizes of the organic nanostructures on wires, tubes, and rods. Through field emission studies, we demonstrate that the films made from arrays of CT complexes are a new kind of cathode materials, and we systematically investigate the effects of size and morphology on electrical properties. Low-dimension organic/inorganic hybrid nanostructures can be used to produce new classes of organic/inorganic solid materials with properties that are not observed in either the individual nanosize components or the larger bulk materials. We developed the combined self-assembly and templating technique to construct various nanostructured arrays of organic and inorganic semiconductors. The combination of hybrid aggregate nanostructures displays distinct optical and electrical properties compared with their individual components. Such hybrid structures show promise for applications in electronics, optics, photovoltaic cells, and biology. In this Account, we aim to provide an intuition for understanding the structure-function relationships in organic molecular materials. Such principles could lead to new design concepts for the development of new nonhazardous, high-performance molecular materials on aggregate nanostructures.     

Symmetry of Bioinspired Short Peptide Nanostructures and Their Basic Physical Properties

Supramolecular bioinspired peptide nanostructures are considered as a new frontier in materials science and engineering. The nano-crystalline packing of various peptide nanostructures, and especially those lacking a center of symmetry at the nanoscale, give rise to exceptional physical properties. Specifically, native aromatic diphenylalanine (FF) and aliphatic dileucine (LL) based nanotubes, which are related to hexagonal and orthorhombic non-centrosymmetric crystalline groups respectively, exhibit fundamental physical phenomena, such as piezoelectricity and second harmonic generation (SHG). This review covers our latest findings on the physical properties of FF and LL nanostructures. We show that heat treatment at the temperature range of 140–180 °C induces irreversible phase transition in FF and LL nanotubes, wherein all their physical properties and structure at all levels (molecular, electronic, optical, space symmetry, morphology, wettability) change. Using high resolution microscopy tools, based on Kelvin probe force microscopy (KPFM), piezoresponse force microscopy (PFM), and SHG, as well as Raman spectroscopy, we demonstrate that the phase-transition phenomena in FF and LL nanotubes leads to full reconstruction and reassembling of native open-end nanotubes into new fiber-like structures, followed by deep variation of non-centrosymmetric to centrosymmetric space symmetry. As a result, the newly generated centrosymmetric phase in FF and LL nanostructures demonstrates neither piezoelectric effect nor nonlinear optical activity.     

Modeling for predicting strength of carbon nanostructures

We have developed a computational scheme to predict stiffness and strength of carbon nanostructures under various loading modes. The prediction method is based on combined molecular mechanics and molecular dynamics simulations to approach a global energy minimum at a given loading level with a preset temperature tolerance of 10⁻⁶K. We have applied the present method to various carbon nanostructures including carbon nanotubes (CNTs), graphene, CNT with defects, a CNT-graphene junction and pillared graphene nanostructures. For all cases, we have identified the maximum stress and strain at failure of these carbon nanostructures as well as their critical failure modes, and discussed mechanisms that lead to their catastrophic failure.     

Towards nano-organic chemistry: perspectives for a bottom-up approach to the synthesis of low-dimensional carbon nanostructures

Low-dimensional carbon nanostructures, such as nanotubes and graphenes, represent one of the most promising classes of materials, in view of their potential use in nanotechnology. However, their exploitation in applications is often hindered by difficulties in their synthesis and purification. Despite the huge efforts by the research community, the production of nanostructured carbon materials with controlled properties is still beyond reach. Nonetheless, this step is nowadays mandatory for significant progresses in the realization of advanced applications and devices based on low-dimensional carbon nanostructures. Although promising alternative routes for the fabrication of nanostructured carbon materials have recently been proposed, a comprehensive understanding of the key factors governing the bottom-up assembly of simple precursors to form complex systems with tailored properties is still at its early stages. In this paper, following a survey of recent experimental efforts in the bottom-up synthesis of carbon nanostructures, we attempt to clarify generalized criteria for the design of suitable precursors that can be used as building blocks in the production of complex systems based on sp(2) carbon atoms and discuss potential synthetic strategies. In particular, the approaches presented in this feature article are based on the application of concepts borrowed from traditional organic chemistry, such as valence-bond theory and Clar sextet theory, and on their extension to the case of complex carbon nanomaterials. We also present and discuss a validation of these approaches through first-principle calculations on prototypical systems. Detailed studies on the processes involved in the bottom-up fabrication of low-dimensional carbon nanostructures are expected to pave the way for the design and optimization of precursors and efficient synthetic routes, thus allowing the development of novel materials with controlled morphology and properties that can be used in technological applications.     

Multiwall carbon nanotube elastomeric composites: A review

Nanostructured materials gained great importance in the past decade on account of their wide range of potential applications in many areas. A large interest is devoted to carbon nanotubes that exhibit exceptional electrical and mechanical properties and can therefore be used for the development of a new generation of composite materials. Nevertheless, poor dispersion and poor interfacial bonding limit the full utilization of carbon nanotubes for reinforcing polymeric media.In this paper, recent advances on carbon nanotubes and their composites will be presented through results of the author's research, essentially based on filled elastomeric networks. The intrinsic potential of carbon nanotubes as reinforcing filler in elastomeric materials will be demonstrated. It will be shown that, despite a poor dispersion, small filler loadings improve substantially the mechanical and electrical behaviors of the soft matrix. With the addition of 1 phr of multiwall carbon nanotubes in a styrene-butadiene copolymer, a 45% increase in modulus and a 70% increase in the tensile length are achieved. Straining effects investigated by atomic force microscopy and infrared and Raman spectroscopies, provide interesting results for the understanding of the mechanical behavior of these nanotube-based composites. All the experimental data lead to the belief that the orientation of the nanotubes plays a major role in the mechanical reinforcement. The strong restriction in equilibrium swelling in toluene with the MWNT content is not ascribed to filler-matrix interfacial interactions but to the occlusion of rubber into the aggregates. On the other hand, carbon nanotubes impart conductivity to the insulator matrix. Between 2 and 4 phr, the conductivity increases by five orders of magnitude reflecting the formation of a percolating network. Changes in resistivity under uniaxial extension completed by AFM observations of stretched composites bring new insights into the properties of these composites by highlighting the contribution of orientational effects.     

Supramolecular bionanocomposites,part 2: Effects of carbon nanoparticle surface functionality on polylactide crystallization

Two types of supramolecular carbon nanostructures, carbon nanospheres (CNS) and multiwalled carbon nanotubes, (MWCNTs) are investigated for their potential as nanofillers in the bioplastic polylactide (PLA). Modification of the surfaces of both carbon nanostructures by covalent attachment of dodecylamine is accomplished and the effects of this compatibilizing functionality are explored. Crystallization kinetics, thermal properties, and mechanical properties are investigated. Addition of a small amount of carbon to the PLA increases the thermal stability by as much as 20–30°C. Incorporation of the MWCNT and CNS increases the heat distortion temperature by up to 10°C. Speed up in crystallization rate is observed for small to intermediate loading levels; however, at higher nanofiller loading, the rate decreases. Functionalized nanostructures are more effective at increasing crystallization rates than unfunctionalized nanostructures. It is concluded that the dodecylamine (DDA) grafted to the carbon surfaces aids in dispersing the materials and preventing aggregation, thereby providing higher surface area for heterogeneous nucleation of the biopolymer. The resulting materials are composed of the supramolecular carbon nanostructure embedded in a semicrystalline biopolymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Gold nanoparticles grown inside carbon nanotubes: synthesis and electrical transport measurements

The hybrid structures composed of gold nanoparticles and carbon nanotubes were prepared using porous alumina membranes as templates. Carbon nanotubes were synthesized inside the pores of these templates by the non-catalytic decomposition of acetylene. The inner cavity of the supported tubes was used as nanoreactors to grow gold particles by impregnation with a gold salt, followed by a calcination-reduction process. The samples were characterized by transmission electron microscopy and X-ray energy dispersion spectroscopy techniques. The resulting hybrid products are mainly encapsulated gold nanoparticles with different shapes and dimensions depending on the concentration of the gold precursor and the impregnation procedure. In order to understand the electronic transport mechanisms in these nanostructures, their conductance was measured as a function of temperature. The samples exhibit a ‘non-metallic’ temperature dependence where the dominant electron transport mechanism is 1D hopping. Depending on the impregnation procedure, the inclusion of gold nanoparticles inside the CNTs can introduce significant changes in the structure of the tubes and the mechanisms for electronic transport. The electrical resistance of these hybrid structures was monitored under different gas atmospheres at ambient pressure. Using this hybrid nanostructures, small amounts of acetylene and hydrogen were detected with an increased sensibility compared with pristine carbon nanotubes. Although the sensitivity of these hybrid nanostructures is rather low compared to alternative sensing elements, their response is remarkably fast under changing gas atmospheres.     

Electronic and magnetic properties of deformed and defective single wall carbon nanotubes

The combined effect of radial deformation and defects on the properties of semiconducting single wall carbon nanotubes are studied using density functional theory. A Stone-Thrower-Wales defect, a substitutional nitrogen impurity, and a mono-vacancy at the highest curvature side of a radially strained nanotube are considered. The energies characterizing the deformation and defect formation, the band gap energies, and various bond lengths are calculated. We find that there is magneto-mechanical coupling behavior in the nanotube properties which can be tailored by the degree of radial deformation and the type of defect. The carbon nanotube energetics and magnetism are also explained in terms of electronic structure changes as a function of deformation and types of defects present in the structure.     

富勒烯类炭材料作为新型载体在多相催化中的应用

评述了富勒烯类新型炭材料作为金属催化剂的载体在多相催化领域中的潜在应用途径。首先概要介绍这些炭材料在均相和多相催化中一些应用实例,然后分别详细分绍C60分子化合物、单壁纳米炭管和多壁纳米炭管等富勒烯类新型炭材料的催化性能及其应用。     

Fabrication of network films of conducting polymer-linked polyoxometallate-stabilized carbon nanostructures

The ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo₁₂O₄₀³⁻), to form stable anionic monolayers on carbon nanoparticles and multi-wall nanotubes is explored here to produce stable colloidal solutions of polyoxometallate covered carbon nanostructures and to disperse them within conducting polymer, poly(3,4-ethylenedioxythiophene), i.e. PEDOT, or polyaniline multilayer films. By repeated alternate treatments in the colloidal suspension of PMo₁₂O₄₀³⁻-protected carbon nanoparticles or nanotubes, and in the acid solution of a monomer (3,4-ethylenedioxythiophene or aniline), the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional organized arrangements (networks) of interconnected organic and inorganic layers on electrode (e.g. glassy carbon) surfaces. In hybrid films, the negatively charged polyoxometallate-covered carbon nanostructures interact electrostatically with positively charged conducting polymer ultra-thin layers. Consequently, the attractive electrochemical charging properties of conducting polymers, reversible redox behavior of polyoxometallate, as well as the mechanical and electrical properties of carbon nanoparticles or nanotubes can be combined. The films are characterized by fast dynamics of charge transport, and they are of potential importance to electrocatalysis and charge storage in redox capacitors.     

Imaging defects and junctions in single-walled carbon nanotubes by voltage-contrast scanning electron microscopy

Voltage-contrast scanning electron microscopy is demonstrated as a new technique to locate and characterize defects in single-walled carbon nanotubes. This method images the surface potential along and surrounding a nanotube in device configuration and it is used here to study the following: (a) structural point-defects formed during nanotube growth, (b) nano-scale gap formed by high-current electrical breakdown, (c) electronic defect such as electron-irradiation induced metal-insulator transition, and (d) charge injection into the substrate which causes hysteresis in nanotube devices. The in situ characterization of defect healing under high bias is also shown. The origin of voltage-contrast, the influence of the above defects on the contrast profiles and optimum imaging conditions are discussed.     

Correlation between atomistic morphology and electron transport properties in defect-free and defected graphene nanoribbons: An interpretation through Clar sextet theory

Structural, electronic and transport properties of defect-free, defected and functionalized armchair and zig-zag graphene nanoribbons (GNRs) are investigated with density functional theory and non-equilibrium Green’s function calculations and rationalized in terms of Clar’s theory of the aromatic sextet. Calculations suggest a tight relationship between the transport properties of nanoribbons and the underlying bond patterning as described by valence bond and Clar sextet theory. Namely, armchair GNRs exhibit a strong dependence of the transport properties on the ribbon width, as a consequence of different valence bond representations. The occurrence of localized defects involving electron pairs does not significantly alter this behavior. Conversely, transport properties of zigzag GNRs are less affected by morphological details, such as width and occurrence of defects, as expected from the application of Clar’s theory. However, controlled edge functionalization and morphology modifications in zigzag GNRs can potentially lead to localization of aromatic sextets and, consequently, to strong changes in the transport properties. Our work indicates Clar sextet theory as a powerful and accurate tool to rationalize and predict the electronic and transport properties of complex carbon nanostructures based on GNRs. These principles can be extended to the design of novel systems with potential applications in nanoelectronics.     

Analytical study of electronic quantum transport in carbon-based nanomaterials

We introduce a new method based on the tight-binding model and mode space (MS) renormalization approach to the study of quantum transport properties of carbon-based nanomaterials (CBNs) such as carbon nanotubes (CNTs), graphene nanoribbons (GNRs), superlattice structures and conducting polymers. The calculations are based on the Green's function method, in which the electrical conductance, density of states (DOS) and localization length of the systems are calculated, analytically. Our model and simple formulas are useful to study the impact of slice-like defects, to distinguish different regimes and reduce the computation time. The efficiency of our method in reducing the CPU time is tested in electrical conductance, where the computation time is reduced by up to a factor of 40 depending on the parameters of the problem. We demonstrate the power of this approach by studying the electronic transport in partially unzipped carbon nanotubes (UCNTs).     

Fluidized bed catalytic chemical vapor deposition synthesis of carbon nanotubes—A review

Carbon nanotubes (CNTs) are pure carbon in nanostructures with unique physico-chemical properties. They have brought significant breakthroughs in different fields such as materials, electronic devices, energy storage, separation, sensors, etc. If the CNTs are ever to fulfill their promise as an engineering material, commercial production will be required. Catalytic chemical vapor deposition (CCVD) technique coupled with a suitable reactor is considered as a scalable and relatively low-cost process enabling to produce high yield CNTs. Recent advances on CCVD of CNTs have shown that fluidized-bed reactors have a great potential for commercial production of this valuable material. However, the dominating process parameters which impact upon the CNT nucleation and growth need to be understood to control product morphology, optimize process productivity and scale up the process. This paper discusses a general overview of the key parameters in the CVD formation of CNT. The focus will be then shifted to the fluidized bed reactors as an alternative for commercial production of CNTs.     

Defect-related hysteresis in nanotube-based nano-electromechanical systems

The electronic properties of multi-walled carbon nanotubes (MWCNTs) depend on the positions of their walls with respect to neighboring shells. This fact can enable several applications of MWCNTs as nano-electromechanical systems (NEMS). In this article, we report the findings of a first-principles study on the stability and dynamics of point defects in double-walled carbon nanotubes (DWCNTs) and their role in the response of the host systems under inter-tube displacement. Key defect-related effects, namely, sudden energy changes and hysteresis, are identified, and their relevance to a host of MWCNT-based NEMS is highlighted. The results also demonstrate the dependence of these effects on defect clustering and chirality of DWCNT shells.