Tailoring (n,m) structure of single-walled carbon nanotubes by modifying reaction conditions and the nature of the support of CoMo catalysts.

The (n,m) population distribution of single-walled carbon nanotubes obtained on supported CoMo catalysts has been determined by photoluminescence and optical absorption. It has been found that the (n,m) distribution can be controlled by varying the gaseous feed composition, the reaction temperature, and the type of catalyst support used. When using CO as a feed over CoMo/SiO2 catalysts, increasing the synthesis temperature results in an increase in nanotube diameter, without a change in the chiral angle. By contrast, by changing the support from SiO2 to MgO, nanotubes with similar diameter but different chiral angles are obtained. Finally, keeping the same reaction conditions but varying the composition of the gaseous feed results in different (n,m) distribution. The clearly different distributions obtained when varying catalysts support and/or reaction conditions demonstrate that the (n,m) distribution is a result of differences in the growth kinetics, which in turn depends on the nanotube cap-metal cluster interaction.

Single-walled carbon nanotubes of controlled diameter and bundle size and their field emission properties.

Field emission studies were conducted on as-produced CoMoCAT single-walled carbon nanotube/silica composites with controlled nanotube diameter and bundle size. It has been observed that the as-produced nanotube material does not need to be separated from the high-surface area catalyst to be an effective electron emitter. By adjusting the catalytic synthesis conditions, single-walled carbon nanotubes (SWNT) of different diameters and bundle sizes were synthesized. A detailed characterization involving Raman spectroscopy, optical absorption (vis-NIR), SEM, and TEM was conducted to identify the nanotube species present in the different samples. The synthesis reaction temperature was found to affect the nanotube diameter and bundle size in opposite ways; that is, as the synthesis temperature increased the nanotube average diameter became larger, but the bundle size became smaller. A gradual and consistent reduction in the emission onset field was observed as the synthesis temperature increased. It is suggested that the bundle size, more than the nanotube diameter or chirality, determines the field emission characteristics of these composites. This is a clear demonstration that field emission characteristics of SWNT can be controlled by the nanotube synthesis conditions.

Decomposition of carbon-containing compounds on solid catalysts for single-walled nanotube production.

Different catalyst formulations and reaction conditions have been used to test the validity of a hypothesis that tries to elucidate the mechanism of single-walled nanotube (SWNT) formation by CO disproportionation over a highly selective cobalt-molybdenum catalyst. This model proposed an intrinsic dependence between the selectivity of the catalysts toward SWNT and the stabilization of Co species in a nonmetallic state, which in turn results from an interaction with Mo. The series of tests performed to examine this model include the doping of this highly selective catalyst with sodium, the substitution of molybdenum by tungsten in the original catalyst formulation, the variation on reaction temperature, and the introduction of hydrogen in the gas feedstock. All these modifications were carried out to modify the growth conditions in which the SWNTs are formed. The results are consistent with the hypothesis proposed by the authors.

Narrow (n,m)-distribution of single-walled carbon nanotubes grown using a solid supported catalyst.

Unusually structure-selective growth of single-walled carbon nanotubes (SWNTs) has been attained using a CVD method with a solid supported catalyst. In this method, CO feedstock disproportionates on silica-supported catalytic nanoclusters of Co that are formed in situ from mixed salts of Co and Mo. The nanotube products are analyzed by spectrofluorimetry to reveal distributions resolved at the level of individual (n,m) structures. Two structures, (6,5) and (7,5), together dominate the semiconducting nanotube distribution and comprise more than one-half of that population. The average diameter of produced SWNTs is only 0.81 nm, and a strong propensity is found favoring chiral angles near the armchair limit.