Molecular dynamics of reactions between (4,0) zigzag carbon nanotube and hydrogen peroxide under extreme conditions

ABSTRACT

Single-wall carbon nanotubes (CNTs) have been suggested as potential materials for use in next-generation gas sensors. The sidewall functionalisation of CNTs facilitates gas molecule adsorption. In this study, density functional theory (DFT)-based ab initio molecular dynamics simulations are performed for a periodic zigzag single-wall (4,0) CNT surrounded by a monolayer of hydrogen peroxide molecules in an attempt to find conditions that favour sidewall functionalisation. The dependency of dynamics on charge states of the system is examined. It is found negative charges favour reactions that result in the functionalisation of the CNT. First principles molecular dynamics of defect formation yields chemically reasonable structure of stable defects, which can be reproduced in CNTs of any diameter and chirality. The explored hydroxyl and hydroperoxyl defects increase conductivity in a large diameter (10,0) CNT, while decrease conductivities in a small diameter (4,0) CNT.     

Realization, characterization and functionalization of lipidic wrapped carbon nanotubes

Mass-produced carbon nanotubes (CNTs) are strongly aggregated and highly hydrophobic, and processes to make them water soluble are required for biological applications. Both covalent and non-covalent strategies are pursued for obtaining stable, highly concentrated CNT aqueous dispersions. Covalent functionalization has the great disadvantage of producing an irreversible chemical modification of nanotubes, thus alterating their mechanical, chemical and electric properties. On the other hand, non-covalent functionalization is often obtained by employing surfactants that sensibly affect cell viability. Moreover, derivatization with biological moieties is often impossible through non-covalent CNT dispersion. This paper proposes a non-covalent dispersion of multi-wall CNT based on a lipidic mixture that can guarantee high concentration and high stability as well as high cytocompatibility. Moreover, CNTs wrapped with a lipid membrane are realized to demonstrate that the proposed CNTs can be functionalised with a dodecapeptide that specifically recognizes activated platelets without chemical modification of the nanotube itself.     

First-principles study of palladium atom adsorption on the boron- or nitrogen-doped carbon nanotubes

We have performed first-principles calculation to investigate the adsorption of a single palladium atom on the surface of the pristine and boron- or nitrogen-doped carbon nanotubes (CNTs). The results show that for the adsorption of a single palladium atom on the pristine CNT surface, the most stable site is Bridge1 site above the axial carbon–carbon bond. Either boron- or nitrogen-doped CNTs can assist palladium surface adsorption, but the detailed mechanisms are different. The enhanced palladium adsorption on boron-doped CNT is attributed to the palladium d orbital strongly hybridized with both boron p orbital and carbon p orbital. The enhancement in palladium adsorption on nitrogen-doped CNT results from activating the nitrogen-neighboring carbon atoms due to the large electron affinity of nitrogen. Furthermore, the axial bond is preferred over the zigzag bond for a palladium atom adsorbed on the surface of all three types of CNTs. The most energetically favorable site for a palladium atom adsorbed on three types of CNTs is above the axial boron–carbon bond in boron-doped CNT. The enhancement in palladium adsorption is more significant for the boron-doped CNT than it is for nitrogen-doped CNT with a similar configuration. So we conclude that accordingly, the preferred adsorption site is determined by the competition between the electron affinity of doped and adsorbed atoms and preferred degree of the axial bond over the zigzag bond.     

Adjustable thermal conductivity in carbon nanotube nanofluids

Homogeneous and stable nanofluids have been produced by suspending well dispersible multi-walled carbon nanotubes (CNTs) into ethylene glycol base fluid. CNT nanofluids have enhanced thermal conductivity and the enhancement ratios increase with the nanotube loading and the temperature. Thermal conductivity enhancement was adjusted by ball milling and cutting the treated CNTs suspended in the nanofluids to relatively straight CNTs with an appropriate length distribution. Our findings indicate that the straightness ratio, aspect ratio, and aggregation have collective influence on the thermal conductivity of CNT nanofluids.     

A novel approach to improve the field emission characteristics of printed CNT films

A novel post-treatment method, including hard hairbrush and electrical treatment, is performed intentionally to improve the field emission capability and stability of screen-printed carbon nanotubes （CNTs）. Compared with untreated films, the field emission properties of the treated ones are greatly enhanced. Scanning electron microscopy （SEM） and Raman spectrum studies reveal that field emission properties are enhanced by two factors. Firstly, the improved field emission properties of CNT films can be attributed to the more active CNT surface by removing the organic material cover on the CNTs. Secondly, the gener- ation of a high density of structural defects and the lower resistance contact to the topside CNT emitters after treatment are all helpful to improving the field emission properties of the treated CNTs.     

Improved emission uniformity and stability of printed carbon nanotubes in electrolyte

In this paper, we studied the effect of NaCl electrolyte as a surface treatment on improving the uniformity and stability of field emission of screen-printed carbon nanotubes (CNTs). A short period of the electrolyte treatment of CNT films remarkably increase emission uniformity and stability. Furthermore, the field emission characteristics of screen-printed carbon nanotubes (CNTs) such as low turn-on field, high emission current density and strong adhesion of the CNT film on the substrate were also reinforced after post-treated. SEM, TEM and Raman spectrum study revealed that uniformity and stability of field emission is enhanced by two factors. Firstly, the electrolyte treatment appeared to render the CNT surfaces more actively by exposing more CNTs form the CNT paste, which dominates initial uniformity and stability of field emission. Secondly, the number of opened CNTs and defects CNTs of CNT film were increased by electrical current energy.     

Control of morphology for energy dissipation in carbon nanotube forests

This study focuses on the effect of carbon precursor on the carbon nanotube (CNT) morphology and energy dissipation. Benzene, toluene, and m-xylene were used as carbon precursors for the synthesis of CNT forests following a chemical vapor deposition process. The results indicate that substituents on the benzene ring increase entanglement in the CNT forests. The absorbed energy was slightly greater for CNT forests synthesized using m-xylene than for toluene, but was much smaller for benzene. When compressed to a strain of 0.67, the toluene CNTs absorbed more energy than the m-xylene CNTs. The restitution was much higher for the forests synthesized with m-xylene than toluene while it further decreased for the forests made with benzene. A strong correlation is also observed between the average diameter of the CNTs and the number of methyl substituents on the benzene ring. The control of the entanglement of the CNT forests can potentially be used to design high energy absorbing composites for blast energy dissipation.     

On the mechanism of carbon nanotube formation: the role of the catalyst

This work examines the recent developments in non-traditional catalyst-assisted chemical vapour deposition of carbon nanotubes (CNTs) with a view to determining the essential role of the catalyst in nanotube growth. A brief overview of the techniques reliant on the structural reorganization of carbon to form CNTs is provided. Additionally, CNT synthesis methods based upon ceramic, noble metal, and semiconducting nanoparticle catalysts are presented. Experimental evidence is provided for CNT growth using noble metal and semiconducting nanoparticle catalysts. A model for CNT growth consistent with the experimental results is proposed, in which the structural reorganization of carbon to form CNTs is paramount.     

Carbon nanotube field emission cathodes fabricated with chemical displacement plating

A new approach for making field emission cathodes consisting of carbon nanotubes (CNTs) is discussed. The authors used a chemical displacement technique to fabricate field emission cathodes by co-depositing CNTs/nickel composite onto the surface of a zinc-coated soda-lime glass. There are several advantages of this displacement method for preparing field emission cathodes such as the uniform distribution of CNTs in the composite cathodes, low cost of consumed CNTs, low cost of instrument and equipment, feasibility of large-area mass production, and stability of plating solution, which can be used for many times and still remain useful after a long-time storage. The results show that, after the CNT purification and dispersion processes, a CNT content of 1.0 g/L, a pH value of 7.0, and a temperature of 50 ± 3 °C are the optimal process conditions which give better CNT distribution in the CNTs/Ni composite emitter and better field emission performance. The CNTs/Ni composite deposited with a plating solution which has been used for tens of times has an emission effect similar to those deposited with a new solution.     

Threshold barrier of carbon nanotube growth

A previously overlooked step of carbon nanotube (CNT) growth, incorporating C atoms into the CNT wall through the CNT-catalyst interface, is studied by density functional theory calculations. A significant barrier for incorporating C atoms into the CNT wall (～2 eV for most used catalysts, Fe, Co, and Ni) is revealed and the incorporation can be the threshold step of CNT growth in most experiments. In addition, the temperature dependent CNT growth rate is calculated and our calculation demonstrates that growing 0.1-1?m long CNTs in 1?h is theoretically possible.     

A cytosine-assisted carbon nanotubes junction: DFT studies

Since nucleobase-functionalized carbon nanotubes (CNTs) are important in the biological applications; the junction of a pair of CNTs through a bridging cytosine linkage is investigated based on density functional theory (DFT) calculations. In the exact model of study, the CNTs are bound to N₁ and C₅ atomic sites of cytosine to make possible the CNT–cytosine–CNT model. To systematically investigate the purpose, the models of original CNT, original cytosine, and primary models of cytosine–CNT in which one CNT is only bound to N₁ or C₅ atomic site of cytosine are also considered. The results of dipole moments and binding energies indicated that the CNT–cytosine–CNT model is the most stable one among all three possible models cytosine-functionalized CNT. The values of energy gaps indicated that the conducting properties of primary cytosine–CNT models are not changed referring to the original CNT but better conductivity could be observed for the CNT–cytosine–CNT model. The values of evaluated quadrupole coupling constants indicated that the electronic densities of nitrogen and oxygen atoms of cytosine detect notable affects during the functionalization processes by the zigzag CNTs and the oxygen atom of CNT–cytosine–CNT model could be proposed as the most proper interacting site of cytosine among other functionalized zigzag models and also the original cytosine. However, the changes of quadrupole coupling constants for the atoms of cytosine are almost negligible during the functionalization processes by the armchair CNTs.     

Aligned carbon nanotube from catalytic chemical vapor deposition technique for energy storage device: a review

Carbon nanomaterial especially carbon nanotube (CNT) possesses remarkably significant achievements towards the development of sustainable energy storage applications. This article reviews aligned CNTs grown from chemical vapor deposition (CVD) technique as electrode material in batteries and electrochemical capacitors. As compared to the entangled CNTs, aligned or well-organized CNTs have advantages in specific surface area and ion accessibility in which more electrolyte ions can access to CNT surfaces for better charge storage performance. CVD known as the most popular technique to produce CNTs enables the use of various substrates and CNT can grow in a variety of forms, such as powder, films, aligned or entangled. Also, CVD is a simple and economic technique, and has good controllability of direction and CNT dimension. High purity of as-grown CNTs is also another beauty of the CVD technique. The current trend and performance of devices utilizing CNTs as electrode material is also extensively discussed.     

Synthesis of Pt-Ni-Fe/CNT/CP nanocomposite as an electrocatalytic electrode for PEM fuel cell cathode

In order to use carbon nanotube (CNT)-supported catalyst as fuel cell electrodes, Pt-Ni-Fe/CNT/carbon paper (CP) electrode was prepared using an ethylene glycol reduction method. CNTs were directly synthesized on Ni-impregnated carbon paper, plain carbon cloth, and Teflonized carbon cloth using chemical vapor deposition. FESEM and TEM images and thermogravimetric analysis indicated that in situ CNT on carbon paper (ICNT/CP) possesses more appropriate structural quality and stronger adhesion to the substrate than other substrates. The contact angle analysis demonstrated that the degree of ICNT/CP surface hydrophobicity encountered a 24% increase in comparison to CP and promoted to superhydrophobicity from hydrophobicity. The polarization curves and electrochemical impedance spectroscopy results of the loaded Pt-Ni-Fe on in situ and ex situ CNT/CP illustrated that the power density increased and charge transfer resistance reduced compared to commercial Pt/C loaded on CP. The results can be attributed to the outstanding properties of CNTs and high catalytic activity of triple catalysts causing alloying of Pt with Ni and Fe, which makes them a proper candidate to be used as cathode electrodes in proton exchange membrane fuel cells.     

The interaction between unique hyperbranched polyaniline and carbon nanotubes,and its influence on the dielectric behavior of hyperbranched polyaniline/carbon nanotube/epoxy resin composites

Novel hybridized multi-walled carbon nanotubes (CNTs), consisting of a unique hyperbranched polyaniline (HSiPA) and CNTs, were prepared. The interaction between HSiPA and CNTs was investigated by many techniques, and results show that there are strong π–π and electrostatic interactions between HSiPA and CNTs, so HSiPA can stack firmly onto the surface of CNTs to form a coating. Based on this, a new kind of ternary composites made up of hybridized CNTs and epoxy (EP) resin was prepared, the influence of the ratio of HSiPA to CNTs on the structure and properties of the HSiPA/CNT/EP composites was intensively studied. The percolation threshold of HSiPA/CNT/EP composites is very low (1.26 wt%); besides, with a suitable ratio of HSiPA to CNTs, the HSiPA/CNT/EP composite has much higher dielectric constant and lower dielectric loss than the CNT/EP composite with the same loading of CNTs. When the ratio of HSiPA to CNTs is 0.5:1, the dielectric constant and loss at 100 Hz of the resultant HSiPA/CNT0.5/EP composite are 711 and 1.53, about 7.1 and 4.3 × 10^?3 times the corresponding value of CNT0.5/EP composite, respectively. In addition, compared with traditional CNT/EP composites, the HSiPA/CNT0.5/EP composites have different equivalent circuit models. These attractive results are attributed to unique structure of hybridized CNTs, and thus leading to greatly different structures between the CNT0.5/EP and HSiPA/CNT0.5/EP composites. This investigation reported herein suggests a new approach to prepare new CNTs and related composites with controllable dielectric properties.     

Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

关于碳纳米管反常反斯托克斯拉曼(AASR)光谱现象的研究

在碳纳米管中观察到了反常反斯托克斯拉曼（ＡＡＳＲ）光谱现象,并发现ＡＡＳＲ现象与碳纳米管的管层数和碳材料的片层样结构无关,因而揣测它可能只与碳纳米管的管状结构有联系。     

Fabrication of a carbon nanotube device using a patterned electrode and a local electric field

Suspensions of carbon nanotubes (CNTs) and organic solvent were dropped onto a substrate which had patterned electrodes while applying a DC voltage between the electrodes. Both multiwall and single-wall (SW) CNTs were purified from the mixture of CNTs and the undesirable particles of carbon when the solvent dichloromethane was used at high temperature. It is found that a SW CNT bridges the gap of the electrodes. This enables us to fabricate CNT devices at a controlled position.     

Carbon nanotube as the core of conical carbon fiber: fabrication,characterization and field emission property

Conical carbon fibers (CCFs) with carbon nanotubes (CNTs) as their cores were grown on graphite substrates with a chemical vapor deposition method. The CNT-cored CCFs were about several tens of micrometers in length. In the interaction with a probe system, the CNT core filaments demonstrated good mechanical strength. Furthermore, field emission currents around 100 μA were also attained from individual CNTs. The growth mechanism of this CNT/CCF combined structure is briefly discussed. Our method has provided a convenient and inexpensive approach to mass assembling CNTs to a carbon substrate. PACS 81.05.Uw; 81.15.Gh; 79.70.+q     

Coupled process of plastics pyrolysis and chemical vapor deposition for controllable synthesis of vertically aligned carbon nanotube arrays

Efficient conversion of waste plastics into advanced materials is of conspicuous environmental, social and economic benefits. A coupled process of plastic pyrolysis and chemical vapor deposition for vertically aligned carbon nanotube (CNT) array growth was proposed. Various kinds of plastics, such as polypropylene, polyethylene, and polyvinyl chloride, were used as carbon sources for the controllable growth of CNT arrays. The relationship between the length of CNT arrays and the growth time was investigated. It was found that the length of aligned CNTs increased with prolonged growth time. CNT arrays with a length of 500 μm were obtained for a 40-min growth and the average growth rate was estimated to be 12 μm/min. The diameter of CNTs in the arrays can be modulated by controlling the growth temperature and the feeding rate of ferrocene. In addition, substrates with larger specific surface area such as ceramic spheres, quartz fibers, and quartz particles, were adopted to support the growth of CNT arrays. Those results provide strong evidence for the feasibility of conversion from waste plastics into CNT arrays via this reported sustainable materials processing.     

Measurement of multi-wall carbon nanotube penetration through a screen filter and single-fiber analysis

In this study, we carried out experiments to study penetration of airborne carbon nanotubes (CNTs) through a screen filter. An electrospray system was employed to aerosolize suspensions of multi-wall CNTs. The generated airborne CNTs were characterized by electron microscopy, and the length and diameter were measured. In the filtration experiments, the challenging CNTs are classified by a differential mobility analyzer. Monodisperse CNTs with the same electrical mobility were then employed to challenge the screen filter. Penetration was measured for CNTs in the range of 100–400 nm mobility diameters. The results showed that the CNT penetration was less than the penetration for a sphere with the same mobility diameter, which was mainly due to the larger interception length of the CNTs. We compared the modeling results using single-fiber filtration efficiency theories with the experimental data, and found that the effective interception length can be approximated by the CNT aerodynamic diameter multiplying a scaling factor. A hypothesis is proposed to understand the observation.