An original growth mode of MWCNTs on alumina supported iron catalysts

Multi-walled carbon nanotubes (MWCNTs) have been produced from ethylene by Fluidized Bed Catalytic Chemical Vapor Deposition (FB-CCVD) on alumina supported iron catalyst powders. Both catalysts and MWCNTs-catalyst composites have been characterized by XRD, SEM-EDX, TEM, Mössbauer Spectroscopy, TGA and nitrogen adsorption measurements at different stages of the process. The fresh catalyst is composed of amorphous iron (III) oxide nanoparticles located inside the porosity of the support and of a micrometric crystalline &-iron (III) oxide surface film. The beginning of the CVD process provokes a brutal reconstruction and simultaneous carburization of the surface film that allows MWCNT nucleation and growth. These MWCNTs grow aligned between the support and the surface catalytic film, leading to a uniform consumption and uprising of the film. When the catalytic film has been consumed, the catalytic particles located inside the alumina porosity are slowly reduced and activated leading to a secondary MWCNT growth regime, which produces a generalized grain explosion and entangled MWCNT growth. Based on experimental observations and characterizations, this original two-stage growth mode is discussed and a general growth mechanism is proposed