Sulphate-activated growth of bamboo-like carbon nanotubes over copper catalysts

A sulphate-activated mechanism is proposed to describe the growth of bamboo-like carbon nanotubes (CNTs) over copper catalysts using chemical vapour deposition with helium-diluted ethylene. Sulphate-assisted copper catalysts afford a high-yield growth of bamboo-like CNTs at a mild temperature, 800 °C; however, non-sulphate-assisted copper catalysts, e.g., copper acetate and copper nitrate prepared catalysts, were inert to CNT growth and only gave amorphous carbons (a-C) surrounding copper nanoparticles under the same conditions. Nevertheless, the addition of sulphate ions in the preparation step for the two inert catalysts can activate their abilities for CNT growth with remarkable yields. Furthermore, Raman spectra analysis demonstrates a linear dependence between the concentration of sulphate ions in copper catalysts and the ratio of CNT-a-C in the as-grown carbon soot. The sulphate-activated effect on CNT growth over copper catalysts could be related to a three-way interaction of sulphate ions, copper nanoparticles and support. In situ TEM images of an as-grown CNT irradiated by electron beams without the inlet of carbon sources reveal a new pathway of carbon diffusion through the bulk of copper nanoparticles and an enlarged inner-wall thickness of the on-site CNT. This carbon diffusion model over copper catalysts can provide new insights into the CNT growth mechanism over non-magnetic metal catalysts.