Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions

The establishment of covalent junctions between carbon nanotubes (CNTs) and the modification of their straight tubular morphology are two strategies needed to successfully synthesize nanotube-based three-dimensional (3D) frameworks exhibiting superior material properties. Engineering such 3D structures in scalable synthetic processes still remains a challenge. This work pioneers the bulk synthesis of 3D macroscale nanotube elastic solids directly via a boron-doping strategy during chemical vapour deposition, which influences the formation of atomic-scale “elbow” junctions and nanotube covalent interconnections. Detailed elemental analysis revealed that the “elbow” junctions are preferred sites for excess boron atoms, indicating the role of boron and curvature in the junction formation mechanism, in agreement with our first principle theoretical calculations. Exploiting this material’s ultra-light weight, super-hydrophobicity, high porosity, thermal stability, and mechanical flexibility, the strongly oleophilic sponge-like solids are demonstrated as unique reusable sorbent scaffolds able to efficiently remove oil from contaminated seawater even after repeated use

Comparison of structural changes in nitrogen and boron-doped multi-walled carbon nanotubes

We investigated the effect of the reaction parameters on the structure of multi-walled carbon nanotubes containing different concentrations of nitrogen and boron. The nanotubes were produced using a 'standard' aerosol chemical vapour deposition technique in conjunction with benzylamine, triethylborane, hexane and toluene mixtures. These precursors were thermally decomposed between 800 and 1100 °C under argon at atmospheric pressure. By varying the precursor concentrations, the nitrogen and boron content of the nanotubes could be altered between 0-2.2 and 0-0.5 at.% respectively. Using a typical laboratory-sized 50 cm long tube furnace, yields between 0.3 and 1.5 g of nanotubes/10 min were relatively easily achieved. Moreover, we show that doping carbon nanotubes with heteroatoms, such as B and N, can be used to control nanotube diameters, change their defect density, and manipulate their oxidation resistance within a range of ca. 170 °C. Hence, we show that it is possible to tune nanotube properties within a certain interval and to produce nanotubes with relatively well defined properties in quantities usable for further characterisation and for studying their viability in applications such as composite materials, gas sensors, capacitors, and electronic components. © 2010 Elsevier Ltd. All rights reserved

In situ engineering of NanoBud geometries.

NanoBuds exist in a variety of stable structures. Our studies show that engineering NanoBud geometries is indeed possible and we visualise the transformation of one Nanobud geometry to another using in situ aberration corrected imaging techniques. Such NanoBuds are precursors for generating nanotube junctions which could be used in composite and electronic applications

Scanning tunneling microscopy and spectroscopy of nitrogen doped multi-walled carbon nanotubes produced by the pyrolysis of ferrocene and benzylamine.

In this work, carbon nanotube samples were produced by aerosol chemical vapour deposition from a solution of ferrocene in benzylamine. The multi-walled nanotubes produced by this method were investigated by TEM, SEM/EDS, scanning tunneling microscopy (STM) and tunneling spectroscopy (STS). The dl/dV curves obtained from the STS measurements showed asymmetric density of states (DOS) in nanotubes, with higher DOS above the Fermi energy. These STS measurements and the EDS analysis indicate successful doping with nitrogen originating from the decomposition of benzylamine

Controlled growth of Ni nanocrystals on SrTiO(3) and their application in the catalytic synthesis of carbon nanotubes.

Truncated pyramid-shaped Ni nanocrystals were epitaxially grown on SrTiO(3)(001) surfaces and characterised by scanning tunneling microscopy (STM). These nanocrystals were shown to be catalytically active for the synthesis of carbon nanotubes (CNTs). The narrow size distribution of the Ni nanocrystals results in a similar narrow distribution of CNT diameters

Metal-free chemical vapor deposition growth of graphitic tubular structures on engineered perovskite oxide substrates

All rights reserved.Metal-free growth of carbon nanotubes/fibers (CNT/Fs) using chemical vapor deposition (CVD) on semiconducting and insulating substrates is of interest in the context of the construction of nanoscale electronic devices. However, controllable synthesis of CNT/Fs without the aid of metal catalysts is an ongoing challenge. Here we report the direct CVD synthesis of CNT/Fs on the perovskite oxides SrTiO3 (STO) and Ba0.6Sr0.4TiO3 (BST). A variety of processing steps were used on STO (001) substrates to create a set of six patterns with varying atomic-scale surface roughnesses. These substrates were all subjected to the same CVD growth conditions, and a correlation was found between the surface roughness of the substrates and the density of CNT/Fs. This indicates that nanometer-scale asperities on the substrates act as the catalytically active sites for CNT/F growth. In a separate set of experiments the surfaces of polished polycrystalline BST samples were investigated. The random orientation of the exposed etched facets of the individual grains revealed significantly different catalytic activity for CNT/F growth. Our study demonstrates the great influence of the nature of the crystal surface condition on the catalytic activity of the substrates and is a critical first step towards perovskite oxide catalyst design

Effects of temperature and ammonia flow rate on the chemical vapour deposition growth of nitrogen-doped graphene.

We doped graphene in situ during synthesis from methane and ammonia on copper in a low-pressure chemical vapour deposition system, and investigated the effect of the synthesis temperature and ammonia concentration on the growth. Raman and X-ray photoelectron spectroscopy was used to investigate the quality and nitrogen content of the graphene and demonstrated that decreasing the synthesis temperature and increasing the ammonia flow rate results in an increase in the concentration of nitrogen dopants up to ca. 2.1% overall. However, concurrent scanning electron microscopy studies demonstrate that decreasing both the growth temperature from 1000 to 900 °C and increasing the N/C precursor ratio from 1/50 to 1/10 significantly decreased the growth rate by a factor of six overall. Using scanning tunnelling microscopy we show that the nitrogen was incorporated mainly in substitutional configuration, while current imaging tunnelling spectroscopy showed that the effect of the nitrogen on the density of states was visible only over a few atom distances

Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum

Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120μmmin-1) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials