A lattice dynamical treatment for the total potential energy of single-walled carbon nanotubes and its applications: relaxed equilibrium structure, elastic properties, and vibrational modes of ultra-narrow tubes

In this paper, we propose a lattice dynamic treatment for the total potential energy of single-walled carbon nanotubes (SWCNTs) which is, apart from a parameter for the nonlinear effects, extracted from the vibrational energy of the planar graphene sheet. The energetics, elasticity and lattice dynamics are treated in terms of the same set of force constants, independently of the tube structures. Based upon this proposal, we have investigated systematically the relaxed lattice configuration for narrow SWCNTs, the strain energy, the Young's modulus and Poisson ratio, and the lattice vibrational properties with respect to the relaxed equilibrium tubule structure. Our calculated results for various physical quantities are nicely in consistency with existing experimental measurements. In particular, we verified that the relaxation effect makes the bond length longer and the frequencies of various optical vibrational modes softer. Our calculation provides evidence that the Young's modulus of an armchair tube exceeds that of the planar graphene sheet, and that the large diameter limits of the Young's modulus and Poisson ratio are in agreement with the experimental values of graphite; the calculated radial breathing modes for ultra-narrow tubes with diameters ranging between 2 and 5 angstrom coincide with the experimental results and the existing ab initio calculations with satisfaction. For narrow tubes with a diameter of 20 angstrom, the calculated frequencies of optical modes in the tubule's tangential plane, as well as those of radial breathing modes, are also in good agreement with the experimental measurements. In addition, our calculation shows that various physical quantities of relaxed SWCNTs can actually be expanded in terms of the chiral angle defined for the corresponding ideal SWCNTs.

A sensitive NADH and glucose biosensor tuned by visible light based on thionine bridged carbon nanotubes and gold nanoparticles multilayer

A NADH and glucose biosensor based on thionine cross-linked multiwalled carbon nanotubes (MWNTs) and Au nanoparticles (Au NPs) multilayer functionalized indium-doped tin oxide (ITO) electrode were presented in this paper. The effect of light irradiation on the enhancement of bioelectrocatalytic processes of the biocatalytic systems by the photovoltaic effect was investigated.

Layer-by-layer assembly of carbon nanotubes and Prussian blue nanoparticles: A potential tool for biosensing devices

A promising method for assembling carbon nanotubes (CNTs) and poly(diallyldimethylammonium chloride) protected Prussian blue nanoparticles (P-PB) to form three-dimensional (3D) nanostructured films is proposed. The electrostatic interaction, combined with layer-by-layer self-assembly (LBL), between negatively charged CNTs and positively charged P-PB is strong enough to drive the formation of the 3D nanostructured films. Thus, prepared multilayer films were characterized by ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV).

Alternate assemblies of polyelectrolyte functionalized carbon nanotubes and platinum nanoparticles as tunable electrocatalysts for dioxygen reduction

A novel method based on electrostatic layer-by-layer self-assembly (LBL) technique for alternate assemblies of polyelectrolyte functionalized multi-walled carbon nanotubes (MWNTs) and platinum nanoparticles (PtNPs) is proposed. The shortened MWNTs can be functionalized with positively charged poly(diallyldimethylammonium chloride) (PDDA) based on electrostatic interaction. Through electrostatic layer-by-layer assembly, the positively charged PDDA functionalized MWNTs (PDWNTs) and negatively charged citrate-stabilized PtNPs were alternately assembled on a 3-mercaptopropanesulfonic sodium (NIPS) modified gold electrode and also on other negatively charged surface, e.g. quartz slide and indium-tin-oxide (ITO) plate, directly forming the three-dimensional (3D) nanostructured materials. This is a very general and powerful technique for the assembling three-dimensional nanostructured materials containing carbon nanotubes (CNTs) and nanoparticles. Thus prepared multilayer films were characterized by ultraviolet-visiblenear-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV). Regular growth of the mutilayer films is monitored by UV-vis-NIR.

A novel hybrid based on carbon nanotubes and heteropolyanions as effective catalyst for hydrogen evolution

Heteropolyanions of tungstophosphoric acid (PWA) have been successfully hybridized with carbon nanotubes (CNTs) by a severe mechanical milling. The obtained hybrid is electroactive for hydrogen evolution (HE) at potentials as positive as -0.16 V vs. Ag/AgCl in 0.2 M HClO4 aqueous solution and its electrocatalysis is up to the level of Pt/CNTs (20 wt% Pt) for HE, indicating a vigorous alternative to Pt group metals. The HE mechanism of the hybrid was also studied and it was found that the tungsten oxycarbides are the electroactive components for HE.

Carbon nanotubes and glucose oxidase bionanocomposite bridged by ionic liquid-like unit: Preparation and electrochemical properties

For their biocompatibility and potential bionanoelectronic applications, integration of carbon nanotubes (CNTs) with biomolecules such as redox enzyme is highly anticipated. Therein, CNTs are expected to act not only as an electron transfer promoter, but also as immobilizing substrate for biomolecules. In this report, a novel method for immobilization of biomolecules on CNTs was proposed based on ionic interaction, which is of universality and widespread use in biological system. As illustrated, glucose oxidase (GOD) and single-walled carbon nanotubes (SWNTs) were integrated into a unitary bionanocomposite by means of ionic liquid-like unit on functionalized SWNTs. The resulted bionanocomposite illustrated better redox response of immobilized GOD in comparison of that prepared by weak physical absorption without ionic interaction. As a potential application of concept, the electrochemical detection of glucose was exemplified based on this novel bionanocomposite.

Electrocatalytic reduction of oxygen at multi-walled carbon nanotubes and cobalt porphyrin modified glassy carbon electrode

The multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc-NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O-2 reduction. The reduction peak potential of O-2 is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co-exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MVVNTs/CoTMPyP)(n) prepared by layer-by-layer method were investigated, and the results showed that the peak current of O-2 reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.

Composite film of carbon nanotubes and chitosan for preparation of amperometric hydrogen peroxide biosensor

A new amperometric biosensor for hydrogen peroxide was developed based on cross-linking horseradish peroxidase (HRP) by glutaraldehyde with multiwall carbon nanotubes/chitosan (MWNTs/chitosan) composite film coated on a glassy carbon electrode. MWNTs were firstly dissolved in a chitosan solution. Then the morphology of MWNTs/chitosan composite film was characterized by field-emission scanning electron microscopy. The results showed that MWNTs were well soluble in chitosan and robust films could be formed on the surface. HRP was cross-linked by glutaraldehyde with MWNTs/chitosan film to prepare a hydrogen peroxide biosensor. The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for H2O2 in the absence of a mediator. The linear range of detection towards H2O2 (applied potential: -0.2 V) was from 1.67 x 10(-5) to 7.40 x 10(-4) M with correction coefficient of 0.998. The biosensor had good repeatability and stability for the determination of H2O2. There were no interferences from ascorbic acid, glucose, citrate acid and lactic acid.

Multilayer films of carbon nanotubes and redox polymer on screen-printed carbon electrodes for electrocatalysis of ascorbic acid

Multilayer films containing multiwall carbon nanotubes and redox polymer were successfully fabricated on a screen-printed carbon electrode using layer-by-layer (LBL) assembled method. UV-vis spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy and electrochemical method were used to characterize the assembled multilayer films. The multilayer films modified electrodes exhibited good electrocatalytic activity towards the oxidation of ascorbic acid (AA). Compared with the bare electrode, the oxidation peak potential negatively shifted about 350 mV (versus Ag/AgCl). Furthermore, the modified screen-printed carbon electrodes (SPCEs) could be used for the determination of ascorbic acid in real samples.

Assembly of polyoxometalates on carbon nanotubes paste electrode and its catalytic behaviors

Carbon nanotubes paste (CNTP) electrode was prepared with multi-walled carbon nanotubes and methyl silicone oil. Polyoxometalates (POMs) were assembled on the electrode surface with different methods, and investigated by cyclic voltammetry and Raman spectroscopy. Experiments showed that POMs/CNTP electrode prepared by direct method had better performance. K6P2Mo18O62 center dot 14H(2)O (P2Mo18) assembled CNTP electrode (P2Mo18/CNTP) electrode possessed good reversibility and could catalyze the reduction of bromate and iodate in 0.1 M H2SO4 Solution. Further, the multilayer films of P2Mo18 assembled CNTP electrodes were fabricated by layer-by-layer technique, which showed higher electrocatalytic activities. All these POMs assembled CNTP electrodes prepared exhibited good stability.

Highly active PtRu catalysts supported on carbon nanotubes prepared by modified impregnation method for methanol electro-oxidation

A simple and rapid synthesis method (denoted as modified impregnation method, MI) for PtRu/CNTs (MI) and PtRu/C (MI) was presented. PtRu/CNTs (MI) and PtRu/C (MI) catalysts were characterized by transmission electron microscopy (TEM) and X-ray diffractometry. It was shown that Pt-Ru particles with small average size (2.7 nm) were uniformly dispersed on carbon supports (carbon nanotubes and carbon black) and displayed the characteristic diffraction peaks of Pt face-centered cubic structure.

High-Strength Composite Fibers: Realizing True Potential of Carbon Nanotubes in Polymer Matrix through Continuous Reticulate Architecture and Molecular Level Couplings

Carbon nanotubes have unprecedented mechanical properties as defect-free nanoscale building blocks, but their potential has not been fully realized in composite materials due to weakness at the interfaces. Here we demonstrate that through load-transfer-favored three-dimensional architecture and molecular level couplings with polymer chains, true potential of CNTs can be realized in composites as Initially envisioned. Composite fibers with reticulate nanotube architectures show order of magnitude improvement in strength compared to randomly dispersed short CNT reinforced composites reported before. The molecular level couplings between nanotubes and polymer chains results in drastic differences in the properties of thermoset and thermoplastic composite fibers, which indicate that conventional macroscopic composite theory falls to explain the overall hybrid behavior at nanoscale.

Aharonov-Bohm oscillation and chirality effect in optical activity of single-wall carbon nanotubes

We study the Aharonov-Bohm effect in the optical phenomena of single-wall carbon nanotubes (SWCN) and also their chirality dependence. Especially, we consider the natural optical activity as a proper observable and derive its general expression based on a comprehensive symmetry analysis, which reveals the interplay between the enclosed magnetic flux and the tubule chirality for arbitrary chiral SWCN. A quantitative result for this optical property is given by a gauge invariant tight-binding approximation calculation to stimulate experimental measurements.

Chiral symmetry analysis and rigid rotational invariance for the lattice dynamics of single-wall carbon nanotubes

We provide a detailed expression of the vibrational potential for the lattice dynamics of single-wall carbon nanotubes (SWCNT's) satisfying the requirements of the exact rigid translational as well as rotational symmetries, which is a nontrivial generalization of the valence force model for the planar graphene sheet. With the model, the low-frequency behavior of the dispersion of the acoustic modes as well as the flexure mode can be precisely calculated. Based upon a comprehensive chiral symmetry analysis, the calculated mode frequencies (including all the Raman- and infrared-active modes), velocities of acoustic modes, and the polarization vectors are systematically fitted in terms of the chiral angle and radius, where the restrictions of various symmetry operations of SWCNT's are fulfilled.