En route to controlled catalytic CVD synthesis of densely packed and vertically aligned nitrogen-doped carbon nanotube arrays

The catalytic chemical vapour deposition (c-CVD) technique was applied in the synthesis of vertically aligned arrays of nitrogen-doped carbon nanotubes (N-CNTs). A mixture of toluene (main carbon source), pyrazine (1,4-diazine, nitrogen source) and ferrocene (catalyst precursor) was used as the injection feedstock. To optimize conditions for growing the most dense and aligned N-CNT arrays, we investigated the influence of key parameters, i.e., growth temperature (660, 760 and 860 °C), composition of the feedstock and time of growth, on morphology and properties of N-CNTs. The presence of nitrogen species in the hot zone of the quartz reactor decreased the growth rate of N-CNTs down to about one twentieth compared to the growth rate of multi-wall CNTs (MWCNTs). As revealed by electron microscopy studies (SEM, TEM), the individual N-CNTs (half as thick as MWCNTs) grown under the optimal conditions were characterized by a superior straightness of the outer walls, which translated into a high alignment of dense nanotube arrays, i.e., 5 × 108 nanotubes per mm2 (100 times more than for MWCNTs grown in the absence of nitrogen precursor). In turn, the internal crystallographic order of the N-CNTs was found to be of a ‘bamboo’-like or ‘membrane’-like (multi-compartmental structure) morphology. The nitrogen content in the nanotube products, which ranged from 0.0 to 3.0 wt %, was controlled through the concentration of pyrazine in the feedstock. Moreover, as revealed by Raman/FT-IR spectroscopy, the incorporation of nitrogen atoms into the nanotube walls was found to be proportional to the number of deviations from the sp2-hybridisation of graphene C-atoms. As studied by XRD, the temperature and the [pyrazine]/[ferrocene] ratio in the feedstock affected the composition of the catalyst particles, and hence changed the growth mechanism of individual N-CNTs into a ‘mixed base-and-tip’ (primarily of the base-type) type as compared to the purely ‘base’-type for undoped MWCNTs

Facile processing of zeolite based catalyst support for carbon nanotube synthesis

Before many of the most promising applications of carbon nanotubes can be realized, nanotube characteristics including chirality, length and diameter must be optimised. One of the most important aspects of supported carbon nanotube synthesis is the interaction of the catalyst with the substrate. The highly uniform and dense pore structures of zeolites make them ideally suited for improving carbon nanotube synthesis, but their powder form renders them incompatible with many commonly used and highly developed synthesis techniques. Existing methods for making planar substrates from zeolites are complex and unsuitable for incorporation into carbon nanotube synthesis. We present an investigation into facile methods for forming zeolites into substrates, demonstrating that these are compatible with many different CNT synthesis techniques and even able to support the growth of aligned arrays of CNTs that are hundreds of microns long. These substrates can be easily produced and incorporated into existing CNT synthesis processes and should therefore aid in the use of zeolites in CNT synthesis generally. This method is also compatible with any powder based porous material such as activated alumina or silica gel, allowing the production of substrates with a wide variety of pore size distributions and surface properties. © 2012 Published by Elsevier B.V

Charging and discharging of the electrochemically swelled, aligned carbon nanotube fibers

Aligned carbon nanotube fibers are macroscopic materials with remarkable properties, such as high specific strength, stiffness, extreme flexibility as well as electrical and thermal conductivity. It is demonstrated that when subjected to negative potentials, these structures undergo the process of swelling in which the increase of their external dimension is observed. Swelling is believed to be caused by cation insertion in the process similar to intercalation. The efficiency of swelling was determined both in organic and aqueous solutions of different pH. Chronocoulometry was used as the technique to monitor the charging-discharging processes of swollen ACNT fibers in a presence of different electrolytes, i.e. LiCl, NaCl and KCl. The possibility of performing the charging-discharging cycles multiple times indicates that the swollen ACNT fibers can be considered as an advantageous material for electrodes in ion batteries and supercapacitors

Patterning of carbon nanotube structures by inkjet printing of catalyst

The controlled deposition of carbon nanotubes (CNTs) has many potential applications in areas such as microfluidics and field emission arrays. The use of inkjet printing to deposit catalyst offers numerous advantages for these, particularly the ability to print arbitrary patterns at low cost. We use inkjet technology to deposit iron salts, which act as a catalyst from which CNTs are subsequently grown by chemical vapour deposition. In this study, we study the effect of the iron salt concentration on ink viscosity, as well as the printing quality using optical and electron microscopy. We find that the iron salt concentration has a significant effect on the pattern quality and, most importantly, allows for the production of controllable ringlike shapes with feature size smaller than that achievable by the print-head alone. These shapes are the result of a variation of the coffee-stain effect, and could be useful particularly in fabricating microfluidic devices. We show that iron salts are suitable CNT catalysts for deposition by inkjet printing, and that their concentration is crucial both for print quality as well as for the production of novel patterns by making use of the drying behaviour of the ink. © Springer Science+Business Media, LLC 2012

Three-dimensional carbon nanowall structures

The authors report the growth of carbon nanowalls in freestanding, three-dimensional aggregates by microwave plasma-enhanced chemical vapor deposition. Carbon nanowalls extrude from plasma sites into three-dimensional space. The growth is catalyst-free and not limited by nucleating surfaces. The growth mechanism is discussed and compared with similar carbon nanomaterials. High surface area of as-grown carbon nanowalls indicates a potential for electrochemical applications. Field emission measurements show a low field turn-on and long-term stability. The results establish a scalable production method and possible applications using field emission or high surface area. © 2007 American Institute of Physics

En route to controlled catalytic CVD synthesis of densely packed and vertically aligned nitrogen-doped carbon nanotube arrays

The catalytic chemical vapour deposition (c-CVD) technique was applied in the synthesis of vertically aligned arrays of nitrogendoped carbon nanotubes (N-CNTs). A mixture of toluene (main carbon source), pyrazine (1,4-diazine, nitrogen source) and ferrocene (catalyst precursor) was used as the injection feedstock. To optimize conditions for growing the most dense and aligned N-CNT arrays, we investigated the influence of key parameters, i.e., growth temperature (660, 760 and 860 °C), composition of the feedstock and time of growth, on morphology and properties of N-CNTs. The presence of nitrogen species in the hot zone of the quartz reactor decreased the growth rate of N-CNTs down to about one twentieth compared to the growth rate of multi-wall CNTs (MWCNTs). As revealed by electron microscopy studies (SEM, TEM), the individual N-CNTs (half as thick as MWCNTs) grown under the optimal conditions were characterized by a superior straightness of the outer walls, which translated into a high alignment of dense nanotube arrays, i.e., 5 × 108 nanotubes per mm2 (100 times more than for MWCNTs grown in the absence of nitrogen precursor). In turn, the internal crystallographic order of the N-CNTs was found to be of a 'bamboo'-like or 'membrane'- like (multi-compartmental structure) morphology. The nitrogen content in the nanotube products, which ranged from 0.0 to 3.0 wt %, was controlled through the concentration of pyrazine in the feedstock. Moreover, as revealed by Raman/FT-IR spectroscopy, the incorporation of nitrogen atoms into the nanotube walls was found to be proportional to the number of deviations from the sp2-hybridisation of graphene C-atoms. As studied by XRD, the temperature and the [pyrazine]/[ferrocene] ratio in the feedstock affected the composition of the catalyst particles, and hence changed the growth mechanism of individual N-CNTs into a 'mixed base-and-tip' (primarily of the base-type) type as compared to the purely 'base'-type for undoped MWCNTs. © 2014 Boncel et al

Poly(3,4-ethylenedioxythiophene) growth on the surface of horizontally aligned MWCNT electrode

The process of conjugated polymer deposition on the surface of horizontally aligned multi-walled carbon nanotube, HA-CNT, electrode is described. Poly(3,4-ethylenedioxythiophene), PEDOT, was grown electrochemically under variable conditions in both aqueous and non-aqueous solutions of selected electrolytes. It is shown that the mechanism of nucleation highly depends on the reaction environment. The presence of a surfactant or non-aqueous medium favors the process of progressive nucleation in which the polymer growth is uniform and a homogeneous film of PEDOT is formed. It is demonstrated that the conditions make it is possible to cover the outer walls of individual HA-CNTs instead of forming thick polymer layer. The application of overpotential is proven to be a necessary condition to generate radical cations and cause relatively fast growth of polymer layer

Nitrogen-induced catalyst restructuring for epitaxial growth of multiwalled carbon nanotubes.

The ability to simply and economically produce carbon nanotubes (CNTs) with a defined chiral angle is crucial for the exploitation of nanotubes for their electrical properties. We investigate a diverse range of nitrogen sources for their ability to control CNT chiral angle via epitaxial growth from highly ordered catalyst particles. Through the use of in situ mass and infrared spectrometry, we elucidate the mechanism by which these ordered catalyst particles are formed, showing that ammonia is a key intermediate in the process. Subsequently, the direct addition of a small amount of ammonia to an otherwise standard CNT synthesis is shown to be able to form catalyst particles that grow single chiral angle multiwalled carbon nanotubes. Variation in the ammonia concentration clarifies the catalyst restructuring necessary for the epitaxial growth of carbon nanotubes and subsequent chiral angle control. The simple addition of a nitrogen source is an attractive route for chiral angle control; however, the model also suggests further ways to optimize CNT chiral angle distributions as well as to improve CNT and graphene yield and crystallinity. This understanding also explains the action of ammonia in its widely used role in activating catalyst prior to CNT growth. Finally, this work highlights the uses of novel surface geometries that are achievable through multiphase catalysts

Toxicity and imaging of multi-walled carbon nanotubes in human macrophage cells.

Multi-walled carbon nanotubes (MWNTs) have been proposed for use in many applications and concerns about their potential effect on human health have led to the interest in understanding the interactions between MWNTs and human cells. One important technique is the visualisation of the intracellular distribution of MWNTs. We exposed human macrophage cells to unpurified MWNTs and found that a decrease in cell viability was correlated with uptake of MWNTs due to mainly necrosis. Cells treated with purified MWNTs and the main contaminant Fe(2)O(3) itself yielded toxicity only from the nanotubes and not from the Fe(2)O(3). We used 3-D dark-field scanning transmission electron microscopy (DF-STEM) tomography of freeze-dried whole cells as well as confocal and scanning electron microscopy (SEM) to image the cellular uptake and distribution of unpurified MWNTs. We observed that unpurified MWNTs entered the cell both actively and passively frequently inserting through the plasma membrane into the cytoplasm and the nucleus. These suggest that MWNTs may cause incomplete phagocytosis or mechanically pierce through the plasma membrane and result in oxidative stress and cell death