Density Functional Theory Study of MoO3 Molecule Encapsulated inside Single-walled Carbon Nanotubes~

The binding energies, geometric structures and electronic properties of molybdenum trioxide (MoO3) molecule encapsulated inside (8,0), (9,0), (10,0) and (14,0) single-walled carbon nanotubes (SWNTs) have been investigated using density functional theory (DFT) method. Due to curvature effect, the calculated binding energy values are different, the variation of which indicated that the stability of MoO3 /SWNT systems increases with increasing the radius of SWNTs. At the same time, owing to the presence of MoO3 molecule, the band gap of MoO3 /SWNTs systems decreases. The analysis of density of states (DOS) reveals hybridization between C-2p and Mo-4d and between C-2p and O-2p orbitals near the Fermi level, which results in electron transfer from SWNTs to MoO3 molecule. The present computations suggest that electronic properties of SWNTs can be modified by doping MoO3 molecule.     

Electron transfer in pristine and functionalised single-walled carbon nanotubes

Since their very first days, electron transfer has always played a special role in carbon nanotubes' life. In view of their structural and electronic uniqueness, carbon nanotubes have been proposed either as bulk electrode materials for sensing and biosensing in advanced electrochemical devices, or as molecular-sized electrodes for very fast electrode kinetics investigations. Alternatively, electron transfer has been used to probe the electronic properties of carbon nanotubes by either direct voltammetric inspection or coupling with spectroscopic techniques, ultimately allowing, in the case of true solutions of individual uncut single-walled carbon nanotubes (SWNTs), to single-out their redox potentials as a function of diameter. For their redox properties, as emerged from these studies, SWNTs represent unique building blocks for the construction of photofunctional nanosystems to be used in efficient light energy conversion devices.     

Electrochemical study of single wall carbon nanotubes/graphene/ferritin composite for biofuel cell applications

A single wall carbon nanotubes (SWNTs)/graphene/ferritin/GOx layer on a glassy carbon electrode (GCE) acting as a biofuel cell anode was fabricated using a SWNTs/graphene/ferritin composite as an electron transfer mediator from the enzyme to the electrode. In the presence of glucose, the SWNTs/graphene/ferritin/GOx composite showed a higher current response than SWNTs/graphene/GOx composite and the electrocatalytic oxidation of glucose on the anode increased linearly with increasing concentration of glucose. The highly distributed SWNTs/graphene/ferritin composite acts as a platform for enzyme immobilization resulted in an enhanced electrocatalytic activity towards glucose. The SWNTs/graphene/ferritin composite showed an enhanced electron transfer from enzyme to the electrode; therefore, SWNTs/graphene/ferritin/GOx composite can be used as an anode in biofuel cells.     

Entrapping of exohedral metallofullerenes in carbon nanotubes: (CsC60)n@SWNT nano-peapods

Exohedral C60-based metallofullerenes, CsC60, have been synthesized and successfully encapsulated into single-wall carbon nanotubes (SWNTs) in high yield by reducing C60 molecules into anions. High-resolution transmission electron microscopy (HRTEM) images and in situ electron energy loss spectroscopy (EELS) indicate that Cs atoms and C60 molecules align within SWNTs as CsC60 exohedral metallofullerenes, and that the formal charge state of encaged CsC60 is expressed as Cs+1C60-1. The present peapods with the exohedral metallofullerenes provide a new insight and the possibility to fine-tune the electronic and transport properties of carbon nanotubes.     

Acyclic cucurbit[n]uril molecular containers selectively solubilize single-walled carbon nanotubes in water

Making single-walled carbon nanotubes (SWNTs) soluble in water is a challenging first step to use their remarkable electronic and optical properties in a variety of applications. We report that acyclic cucurbit[n]uril molecular containers 1 and 2 selectively solubilize small-diameter and low chiral angle SWNTs. The selectivity is tunable by increasing the concentration of the molecular containers or by adjusting the ionic strength of the solution. Even at a concentration 1000 times lower than typically required for surfactants, the molecular containers render SWNTs soluble in water. Molecular mechanics simulations suggest that these C-shaped acyclic molecules complex the SWNTs such that a large portion of nanotube sidewalls are exposed to the external environment. These "naked" nanotubes fluoresce upon patching the exposed surface with sodium dodecylbenzene sulfonate.     

Preferred functionalization of metallic and small-diameter single-walled carbon nanotubes by nucleophilic addition of organolithium and -magnesium compounds followed by reoxidation

Covalent sidewall addition to single-walled nanotubes (SWNTs) of a series of organolithium and organomagnesium compounds (nBuLi, tBuLi, EtLi, nHexLi, nBuMgCl, tBuMgCl) followed by reoxidation is reported. The functionalized R(n)-SWNTs were characterized by Raman and NIR emission spectroscopy. The reaction of SWNTs with organolithium and magnesium compounds exhibits pronounced selectivity: in general, metallic tubes are more reactive than semiconducting ones. The reactivity of SWNTs toward the addition of organometallic compounds is inversely proportional to the diameter of the tubes. This was determined simultaneously and independently for both metallic and semiconducting SWNTs. The reactivity also depends on the steric demands of the addend. Binding of the bulky t-butyl addend is less favorable than addition of primary alkyl groups. Significantly, although tBuLi is less reactive than, for example, nBuLi, it is less selective toward the preferred reaction with metallic tubes. This unexpected behavior is explained by fast electron transfer to the metallic SWNTs having low-lying electronic states close to the Fermi level, a competitive initial process. The NIR emission of weakly functionalized semiconducting SWNTs, also reported for the first time, implies interesting applications of functionalized tubes as novel fluorescent reporter molecules.     

Deformation of single‐walled carbon nanotubes by interaction with graphene: A first‐principles study

The interaction between single‐walled carbon nanotubes (SWNTs) and graphene were studied with first‐principles calculations. Both SWNTs and single‐layer graphene (SLG) or double‐layer graphene (DLG) display more remarkable deformations with the increase of SWNT diameter, which implies a stronger interaction between SWNTs and graphene. Besides, in DLG, deformation of the upper‐layer graphene is less than in SLG. Zigzag SWNTs show stronger interactions with SLG than armchair SWNTs, whereas the order is reversed for DLG, which can be interpreted by the mechanical properties of SWNTs and graphene. Density of states and band structures were also studied, and it was found that the interaction between a SWNT and graphene is not strong enough to bring about obvious influence on the electronic structures of SWNTs. © 2015 Wiley Periodicals, Inc.     

Surfactant‐Dependent Charge Transfer between Polyoxometalates and Single‐Walled Carbon Nanotubes: A Fluorescence Spectroscopic Study

Hybridizations of redox‐active polyoxometalates (POMs) with single‐walled carbon nanotubes (SWNTs) have been widely investigated for their diverse applications. For the purpose of constructing high‐quality electronic devices, controlling charge transfer within POM/SWNT hybrids is an inevitable issue. As determined by means of fluorescence spectroscopy, electron transfer between SWNTs and a common POM dopant, phosphomolybdic acid (PMo₁₂), can be tuned simply by an alteration of nanotube surfactant type from anionic to nonionic. The mechanism is attributed to the influence of surfactant type on the stabilization of the electron donor–acceptor hybrid and effect of surfactant–nanotube interactions. These results will be important to control charge‐transport behavior in nanohybrids consisting of carbon nanotubes.     

Antenna chemistry with metallic single-walled carbon nanotubes

We show that, when subjected to microwave fields, surfactant-stabilized single-walled carbon nanotubes (SWNTs) develop polarization potentials at their extremities that readily drive electrochemical reactions. In the presence of transition metal salts with high oxidation potential (e.g., FeCl3), SWNTs drive reductive condensation to metallic nanoparticles with essentially diffusion-limited kinetics in a laboratory microwave reactor. Using HAuCl4, metallic particles and sheaths deposit regioselectively at the SWNT tips, yielding novel SWNT-metal composite nanostructures. This process is shown to activate exclusively metallic SWNTs; a degree of diameter selectivity is observed using acceptors with different oxidation potentials. The reaction mechanism is shown to involve Fowler-Nordheim field emission in solution, where electric fields concentrate at the SWNT tips (attaining approximately 10(9) V/m) due to the SWNT high aspect ratio (approximately 1000) and gradient compression in the insulating surfactant monolayer. Nanotube antenna chemistry is remarkably simple and should be useful in SWNT separation and fractionation processes, while the unusual nanostructures produced could impact nanomedicine, energy harvesting, and synthetic applications.     

Effect of carbon nanotubes on the crystallization and properties of polypropylene

The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005     

Spectroelectrochemistry of carbon nanostructures.

This review is focused on charge-transfer reactions at carbon nanotubes and fullerenes. The spectroelectrochemistry of fullerenes deals with the spin states of fullerenes, the role of mono-anions and the reactivity of higher charged states in C60. The optical (Vis-NIR) spectroelectrochemistry of single-walled carbon nanotubes (SWNTs) follows changes in the allowed optical transitions among the Van Hove singularities. The Raman spectroelectrochemistry of SWNT benefits from strong resonance enhancement of the Raman scattering. Here, both semiconducting and metallic SWNTs are analyzed using the radial breathing mode (RBM) and G-modes as well as the second order (D, G') and intermediate frequency modes. Raman spectroelectrochemistry of SWNT allows the addressing of index-identified tubes and even single isolated nanotubes. Optical and Raman spectroelectrochemistry of fullerene peapods, C60@SWNT and C70@SWNT indicates effective shielding of the intratubular fullerene (peas). The most striking effect in the spectroelectrochemistry of peapods is the so-called "anodic Raman enhancement" of intratubular C60. Double-walled carbon nanotubes (DWNTs) give a specific spectroscopic response in Vis-NIR spectroelectrochemistry for the inner and the outer tube. They are better distinguishable by Raman spectroelectrochemistry which allows a precise tracing of the specific doping response of outer/inner tubes.     

纳米碳管电子结构和键合特性的第一原理研究

利用第一原理方法对一系列尺寸变化的单层纳米碳管电子结构进行了研究,得到了总态密度和态密度随碳管半径R的变化情况与实验结果完全一致,Fermi能级处态密度值随着管径R的增大而减小,说明纳米管的化学活性随着管径的增大而增强。碳管中C-C之间的键合为2s和2p价电子混合而成的弯曲的σ,π键,随着管径R的增大,化学键的弯曲度逐渐减小,C-C之间的键合作用和结合能逐渐增强,电荷密度和对应的势场也逐渐减弱。这些结果表明管径较小的纳米碳管在复合材料的合成中具有一定的优势。     

Carbon nanotubes films: electronic properties and their application as field emitters

Aligned carbon nanotube films have been studied with a wide variety of characterization techniques. Although nanotubes resemble bulk graphite as far as carrier densities, susceptibilities and conductivities are concerned, transport properties and ESR measurments indicate that carrier localization occurs at low temperatures. Nanotube films are good field emitters producing large currents at relatively low electric fields. The performance is superior to the intensely studied CVD diamond films in particular for the threshold field for electron emission. We believe that the observed remarkable electron emission is related to the special electronic structure of the nanotube tips.     

Band‐Gap Opening in Metallic Single‐Walled Carbon Nanotubes by Encapsulation of an Organic Salt

The encapsulation of viologen derivatives into metallic single‐walled carbon nanotubes (SWNTs) results in the opening of a band gap, making the SWNTs semiconducting. Raman spectroscopy, thermogravimetric analysis, and aberration‐corrected high‐resolution transmission electron microscopy confirm the encapsulation process. Through the fabrication of field‐effect transistor devices, the change of the electronic structure of the tubes from metallic to semiconducting upon the encapsulation is confirmed. The opening of a gap in the band structure of the tubes was not detected in supramolecular controls.     

Observation of negative and positive trions in the electrochemically carrier-doped single-walled carbon nanotubes

Understanding of electronic and optical features of single-walled carbon nanotubes (SWNTs) has been a central issue in science and nanotechnology of carbon nanotubes. We describe the detection of both the positive trion (positively charged exciton) and negative trion (negatively charged exciton) as a three-particle bound state in the SWNTs at room temperature by an in situ photoluminescence spectroelectrochemistry method for an isolated SWNT film cast on an ITO electrode. The electrochemical hole and electron dopings enable us to detect such trions on the SWNTs. The large energy difference between the singlet bright exciton and the negative and positive trions showing a tube diameter dependence is determined by both the exchange splitting energy and the trion binding energy. In contrast to conventional compound semiconductors, on the SWNTs, the negative trion has almost the same binding energy to the positive trion, which is attributed to nearly identical effective masses of the holes and electrons.     

Studies of bromine modified single-walled carbon nanotubes using photoelectron spectroscopy and density-functional theory

Many applications based on single-walled carbon nanotubes (SWNTs) require chemical modification of carbon nanotube to optimize the functionalities of the device. In this contribution we discuss the properties of SWNTs immersed in a hydrobromic acid (HBr) solution. Changes of atomic and electronic structures of bromine modified SWNTs were investigated using photoelectron spectroscopy (PES). Spectra of SWNTs before and after immersion in the HBr solution exhibit different features. To understand the mechanism of interaction between SWNTs and bromine, we performed density-functional theory calculations to reveal the structural changes, adsorption energy and chemical bonding information of SWNTs interacting with bromine. In addition, based on the Gelius model, from the molecular orbitals (MOs), we calculated ultraviolet photoelectron spectra (UPS) of SWNTs with and without functionalizing and compared them with the experiment. The present study is a first step in the understanding of the functionalization mechanism of carbon nanotubes.     

Field emission properties of N-doped capped single-walled carbon nanotubes: a first-principles density-functional study

The geometrical structures and field emission properties of pristine and N-doped capped (5,5) single-walled carbon nanotubes have been investigated using first-principles density-functional theory. The structures of N-doped carbon nanotubes are stable under field emission conditions. The calculated work function of N-doped carbon nanotube decreases drastically when compared with pristine carbon nanotube, which means the enhancement of field emission properties. The ionization potentials of N-doped carbon nanotubes are also reduced significantly. The authors analyze the field emission mechanism in terms of energy gap between the lowest unoccupied molecular orbital and the highest occupied molecular orbital, Mulliken charge population, and local density of states. Due to the doping of nitrogen atom, the local density of states at the Fermi level increases dramatically and donor states can be observed above the Fermi level. The authors' results suggest that the field emission properties of carbon nanotubes can be enhanced by the doping of nitrogen atom, which are consistent with the experimental results.     

Formation and structural observation of cesium encapsulated single-walled carbon nanotubes

Cesium encapsulation inside single-walled carbon nanotubes (SWNTs) is for the first time realized by ion irradiation of SWNTs immersed in a magnetized alkali-metal plasma, the configuration of which is confirmed to comprise three varieties by field emission type transmission electron microscopy (FE-TEM) and scanning TEM (STEM) observation.     

Evolution of the molecular structure of metallic and semiconducting carbon nanotubes under laser irradiation

The temperature dependence of the morphology of single wall carbon nanotubes (SWNTs) has been studied by Raman spectroscopy at different temperatures by changing the incident laser power. It is shown that a high power laser irradiation treatment of as-grown samples anneals the SWNTs, improving their structural order and perhaps also removing adsorbed gases. As a result, a significant increase in the Raman cross-section of the nanotubes upon laser irradiation can be observed, for both metallic or semiconducting tubes. The investigation of the power level dependence of the Raman spectra also reveals that smaller diameter nanotubes are burned off first, increasing the mean diameter of the nanotubes in the sample.     

Electronic properties of single-walled carbon nanotubes inside cyclic supermolecules

Possible ways for manipulating carbon nanotubes (CNTs) with cyclic supermolecules are studied using density functional theory. Electronic structure calculations with structure optimizations have been performed for the (4,4) and (8,0) single-walled carbon nanotubes (SWNTs) complexed with crown ethers as well as for the (4,0) SWNT with beta-cyclodextrin. A slight polarization of charge in both the nanotube and the supermolecule is observed upon rotaxane complexation, but the interaction is mainly repulsive, and the systems stay 2.8-3.5 A apart. The supermolecule does not affect the electronic band structure of the nanotube significantly within such a configuration. The situation differs noticeably for chemically cross-linked SWNTs and crown ethers, where a peak arises at the Fermi energy in the density of states. As a result, the band gap of semiconducting CNT(8,0) (0.5 eV) vanishes, and a new conduction channel opens for the metallic CNT(4,4).