The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Effect of catalyst pretreatment on chirality-selective growth of single-walled carbon nanotubes

We show that catalyst pretreatment conditions can have a profound effect on the chiral distribution in single-walled carbon nanotube chemical vapor deposition. Using a SiO2-supported cobalt model catalyst and pretreatment in NH3, we obtain a comparably narrowed chiral distribution with a downshifted tube diameter range, independent of the hydrocarbon source. Our findings demonstrate that the state of the catalyst at the point of carbon nanotube nucleation is of fundamental importance for chiral control, thus identifying the pretreatment atmosphere as a key parameter for control of diameter and chirality distributions. © 2014 American Chemical Society.

The role of the sp2:sp3 substrate content in carbon supported nanotube growth

We report the growth of vertically-aligned nanotube forests, of up to 0.2 mm in height, on an 85:15 sp2:sp3 carbon support with Fe catalyst. This is achieved by purely-thermal chemical vapour deposition with the catalyst pretreated in inert environments. Pretreating the catalyst in a reducing atmosphere causes catalyst diffusion into the support and the growth of defective tubes. Other sp2:sp3 compositions, including graphite, tetrahedral amorphous carbon, and pure diamond, also lead to the growth of defective carbon morphologies. These results pave the way towards controlled growth of forests on carbon fibres. It could give rise to applications in enhanced fuel cell electrodes and better hierarchical carbon fibre-nanotube composites. © 2014 Elsevier Ltd. All rights reserved.