Catalyst-mediated etching of carbon nanotubes exhibiting electronic-structure insensitivity and reciprocal kinetics with growth

Abstract: The selective etching of carbon nanotubes has been widely explored as a post-synthetic route for enriching semiconducting species. As nanoelectronic applications increasingly demand pure semiconducting nanotubes for use in field-effect transistors and other optoelectronic devices, understanding the mechanistic basis of selective removal becomes critical. While etching selectivity is often attributed to electronic structure effects on tube walls, its relevance in the presence of catalyst nanoparticles remains unclear. Here, we directly quantify the catalyst-mediated etching and growth rates of individual single-walled carbon nanotubes using elaborate isotope labeling methods. Surprisingly, in water vapor and methanol environments, catalytic etching proceeds with negligible dependence on tube electronic type, in sharp contrast to non-catalytic oxidation pathways. In-situ Raman analysis upon heating on nanotube ensembles also confirms metallicity-insensitive etching under catalytic conditions, whereas sidewall oxidation without catalysts exhibits pronounced selectivity. Our growth kinetic model, which precisely describes the kinetics of catalytic etching process, motivates kinetic Monte Carlo simulations of nanotube edge dynamics, revealing the reciprocal nature of edge configuration during growth and etching. These findings highlight a fundamental mechanistic distinction between catalytic and non-catalytic reactivity and thus propose that catalytic etching may serve as a diagnostic mirror of growth behavior when using pre-sorted carbon nanotube samples.