Sequential N₂ Adsorption by the Nanopore Entrance Filling Scheme in Nanopores of Carbon Nanotubes

Abstract

The adsorption dynamics and mechanism of nitrogen molecules in 1−7 nm carbon nanotubes (CNTs) at 77 K were investigated by experiments and molecular dynamics simulations. The adsorbed nitrogen amount rapidly increased in 7 nm CNTs, while it gradually increased in 1 and 3 nm CNTs. The gradual increase in 3 nm CNTs was unexpected because of the presence of sufficient adsorption sites and the weak adsorption potential of nitrogen. The molecular dynamics simulations indicated that molecules were condensed in the entrance of nanopores after monolayer adsorption in 3 nm CNTs and monolayer and bilayer adsorption in 5 nm CNTs, called nanopore entrance filling. The proposed adsorption mechanism of nitrogen molecules in CNT nanopores is as follows: first, layer-by-layer adsorption occurs on monolayer sites, followed by preferential adsorption at the nanopore entrance. Consequently, preadsorbed molecules form a fluidic pore neck similar to an ink-bottle pore. Then, newly adsorbed molecules are condensed on the fluidic pore neck, and condensed molecules in the nanopore entrance finally move into the inner part of the nanopore. The proposed sequential adsorption mechanism via nanopore entrance filling without pore blocking starkly differs from micropore filling in micropores and layer-by-layer adsorption associated with capillary condensation in mesopores.

Molecular Simulation of Nitrogen Adsorption in Multidimensional Nanopores and New Insights into the Inversion of Pore Size Distribution for Gas Shale

“…In summary, this study works on statistical adsorption mechanisms, and focuses on the relative pressure of condensation and evaporation feature. The adsorption dynamic is also important and will be investigated in future work [36][37][38].…”