Monolayer aspects of high-resolution αs-plots

The problem of the estimation of high resolution comparative plots (αs method) is revised. Adsorption isotherms of Ar (T = 87 K) are simulated (GCMC) on the bundles of closed and opened multiwalled carbon nanotubes. Those materials are chosen in order to observe the influence of porosity on Ar adsorption, and consequently, on the comparative plots. The introduction of the structural heterogeneity (defects in the external and internal walls of osculating and separated nanotubes) is also studied. The monolayer and multilayer parts of adsorption are extracted from the total amount adsorbed for all studied adsorbents and the reference one (the bundle of the ideal 3-layered carbon tubes with very wide diameters). The significant influence of the distance between carbon nanotubes and defects (in the external and internal walls) is observed on the monolayer αs-plots. In the case of comparative plots calculated for the multilayer adsorption the differences are also visible; however, the expected linear dependence of the amount adsorbed on a porous solid plotted against the amount adsorbed on a reference nonporous solid (the layer-by-layer adsorption occurs on both solid surfaces) in a wide range of relative pressures is not observed. The obtained results demonstrate the complexity of αs method when both microporosity and surface heterogeneity are present. A comparison of isotherms shows that for the studied adsorbents Ar is sensitive to the appearance of the geometrical and structural defects, even at low coverage.