Unraveling the mechanisms of carbon nanotube growth by chemical vapor deposition

[Display omitted] •A new growth mechanism is proposed for the CVD of CNTs.•Model predictions are in good agreement with experimental measurements.•Up to 750 °C, the process is limited by the carbon diffusion through the catalyst.•Above 750 °C, the gas-phase acetylene reaction results in catalyst deactivation.•The catalyst lifetime is investigated for the first time computationally. The mechanisms of carbon nanotube (CNT) growth by chemical vapor deposition of acetylene on Fe/SiO2:Al2O3 (zeolite Y) catalyst are unraveled through a combined computational and experimental study. CNTs are synthesized in a horizontal reactor under atmospheric pressure within the temperature range 650 °C–850 °C and characterized by SEM, TEM and Raman spectroscopy. A macroscopic computational fluid dynamics (CFD) model accounting for fluid flow, heat transfer and species transport is developed for the process, incorporating also kinetic expressions for acetylene surface decomposition, acetylene gas-phase reactions, carbon diffusion through the bulk of the catalyst, carbon surface accumulation on the catalyst surface and eventually, CNTs growth. The experimental behavior of the CNTs growth can be accurately described by the proposed macroscopic model. Most importantly, theoretical predictions suggest that there are two distinct temperature regimes for CNTs formation: at the low temperature regime, the process is dominated by the competition between carbon diffusion through the catalyst and carbon impurity layer formation on the catalyst surface, while at higher temperature, the gas-phase reactions of acetylene prevails, releasing byproducts that deposit on the catalyst surface in the form of carbon impurities. Finally, using the developed computational approach, the catalyst lifetime, which is directly affected by these mechanisms, is correlated with the CNTs growth process.