Fe/Co alloys for the catalytic chemical vapor deposition synthesis of single- and double-walled carbon nanotubes (CNTs). 1. The CNT-Fe/Co-MgO system.

Mg(0.90)Fe(x)Co(y)O (x + y = 0.1) solid solutions were synthesized by the ureic combustion route. Upon reduction at 1000 degrees C in H2-CH4 of these powders, Fe/Co alloy nanoparticles are formed, which are involved in the formation of carbon nanotubes, which are mostly single and double walled, with an average diameter close to 2.5 nm. Characterizations of the materials are performed using 57Fe Mössbauer spectroscopy and electron microscopy, and a well-established macroscopic method, based on specific-surface-area measurements, was applied to quantify the carbon quality and the nanotubes quantity. A detailed investigation of the Fe/Co alloys' formation and composition is reported. An increasing fraction of Co2+ ions hinders the dissolution of iron in the MgO lattice and favors the formation of MgFe2O4-like particles in the oxide powders. Upon reduction, these particles form alpha-Fe/Co particles with a size and composition (close to Fe(0.50)Co(0.50)) adequate for the increased production of carbon nanotubes. However, larger particles are also produced resulting in the formation of undesirable carbon species. The highest CNT quantity and carbon quality are eventually obtained upon reduction of the iron-free Mg(0.90)Co(0.10)O solid solution, in the absence of clusters of metal ions in the starting material.

Fe/Co alloys for the catalytic chemical vapor deposition synthesis of single- and double-walled carbon nanotubes (CNTs). 2. The CNT-Fe/Co-MgAl2O4 system.

A detailed 57Fe Mössbauer study of the Mg(0.8)Fe(0.2-y)Co(y)Al2O4 (y = 0, 0.05, 0.1, 0.15, 0.2) solid solutions and of the CNT-Fe/Co-MgAl2O4 nanocomposite powders prepared by reduction in H2-CH4 has allowed characterization of the different iron phases involved in the catalytic process of carbon nanotube (CNT) formation and to correlate these results with the carbon and CNT contents. The oxide precursors consist of defective spinels of general formulas (Mg(1-x-y)(2+)Fe(x-3alpha)(2+)Fe(2alpha)(3+)[symbol: see text](alpha)Co(y)(2+)Al2(3+))O4(2-) . The metallic phase in the CNT-Fe/Co-MgAl2O4 nanocomposite powders is mostly in the form of the ferromagnetic alpha-Fe/Co alloy with the desired composition. For high iron initial proportions, the additional formation of Fe3C and gamma-Fe-C is observed while for high cobalt initial proportions, the additional formation of a gamma-Fe/Co-C phase is favored. The higher yield of CNTs is observed for postreaction alpha-Fe(0.50)Co(0.50) catalytic particles, which form no carbide and have a narrow size distribution. Alloying is beneficial for this system with respect to the formation of CNTs.

Gram-scale CCVD synthesis of double-walled carbon nanotubes.

Synthesis of clean double-walled carbon nanotubes by a catalytic chemical vapour deposition (CCVD) method is reported; the catalyst is a Mg(1 - x)Co(x)O solid solution containing additions of Mo oxide; this MgO-based catalyst can be easily removed, leading to gram-scale amounts of clean carbon nanotubes, 77% of which are double-walled carbon nanotubes.