Structures of iron and cobalt bimetallic clusters for optimized chemical vapor deposition growth of single-walled carbon nanotubes

We investigate iron-cobalt (Fe-Co) alloys as a representative high-performance catalyst system for SWCNT growth in a systematic manner by combining chemical vapor deposition (CVD) experiments with chirality-resolved spectroscopic analysis, as well as molecular dynamics (MD) simulations based on density functional theory-derived machine learning force fields while varying the Fe-Co ratio. Using zeolite-based SWCNTs prepared by alcohol CVD, absorption and photoluminescence spectroscopy, together with two-dimensional excitation-emission fitting was employed to quantify chirality-specific growth efficiency. Two distinct growth regimes were identified. At a relatively low temperature of 600 C, pure Co exhibits the highest catalytic activity, promoting efficient growth of small-diameter (0.7-0.9 nm) SWCNTs. In contrast, at 850 C, the Fe0.75Co0.25 alloy shows a pronounced enhancement in growth efficiency compared with pure Fe, pure Co, and other Fe-Co compositions, also yielding larger diameter tubes (0.9-1.1nm). Similar growth behavior was observed on SiO2 substrates, enabling detailed transmission electron microscopy analysis of catalyst nanoparticles. Electron microscopy and energy-dispersive X-ray spectroscopy reveal that high SWCNT yields correlate with the formation of small, uniform Fe-Co nanoparticles with Co-enriched surfaces, in excellent agreement with MD simulations. Lastly, MD results are summarized in a composition-diameter phase diagram that rationalizes the experimentally observed growth trends. The exceptional performance of the Fe0.75Co0.25 catalyst at high temperature is attributed to the stabilization of small and uniform catalyst clusters, providing mechanistic insight into the synergistic roles of alloy composition and temperature in SWCNT growth.