Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes.

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. Here, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ± 1.3 nm to 6.4 ± 1.1 nm over 0-800 ppm O₂, and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O₂, and this effect was mitigated by high H₂ concentrations and not due to water vapor (as confirmed in O₂-free water addition experiments), supporting the importance of O₂ specifically. Further characterization of the interface between the Fe catalyst and Al₂O₃ support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Taken as a whole, our results suggest that the impacts of O₂ and H₂ on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.