Low temperature mechanism of adsorption of methane: Comparison between homogenous and heterogeneous pores

The mechanisms of methane adsorption in (i) homogeneous carbon slit pores of widths between 1 nm and 2 nm and (ii) heterogeneous MOF pores of similar unit cell sizes have been compared. We discuss the mechanism of layering transition in subcritical conditions, for temperatures between 80 K and 180 K. The layer formation is strongly temperature-dependent. In slit pores it varies from a sharp adsorption at low temperatures to a more continuous uptake at higher temperatures. The pore size defines the number of adsorbed layers: the 1 nm pore allows adsorption of 2 layers while the 2 nm pore allows adsorption of 5 layers of methane molecules. We compare this behavior with the mechanism of adsorption in two MOFs, IRMOF-1 and IRMOF-16, with strongly heterogeneous walls (both structurally and energetically). This comparison allows us to discuss separately the influence of wall topology and intermolecular interactions on the mechanism of layering. (C) 2015 Elsevier B.V. All rights reserved.