Synthesis of MWCNTs by chemical vapor deposition of methane using FeMo/MgO catalyst: role of hydrogen and kinetic study

This study aims to investigate the role of hydrogen on CNTs synthesis and kinetics of CNTs formation. The CNTs were synthesized by catalytic chemical vapor deposition of methane over FeMo/MgO catalyst. The experimental results revealed that hydrogen plays an important role in the structural changes of catalyst during the pre-reduction process. The catalyst structure fully transformed into metallic FeMo phases, resulting in an increased yield of 5 folds higher than those of the non-reduced catalyst. However, the slightly larger diameter and lower crystallinity ratio of CNTs was obtained. The hydrogen co-feeding during the synthesis can slightly increase the CNTs yield. After achieving the optimum amount of hydrogen addition, further increase in hydrogen would inhibit the methane decomposition, resulting in lower product yield. The hydrogenation of carbon to methane was proceeded in hydrogen co-feed process. However, the hydrogenation was non-selective to allotropes of carbon. Therefore, the addition of hydrogen would not benefit neither maintaining the catalyst stability nor improving the crystallinity of the CNT products. The kinetic model of CNTs formation, derived from the two types of active site of dissociative adsorption of methane, corresponded well to the experimental results. The rate of CNTs formation greatly increases with the partial pressure of methane but decreases when saturation is exceeded. The activation energy was found to be 13.22 kJ mol(-1), showing the rate controlling step to be in the process of mass transfer.