Quasicontinuous Cooperative Adsorption Mechanism in Crystalline Nanoporous Materials

[Image: see text] The hase behavior of confined fluids adsorbed in nanopores differs significantly from their bulk counterparts and depends on the chemical and structural properties of the confining structures. In general, phase transitions in nanoconfined fluids are reflected in stepwise adsorption isotherms with a pronounced hysteresis. Here, we show experimental evidence and an in silico interpretation of the reversible stepwise adsorption isotherm which is observed when methane is adsorbed in the rigid, crystalline metal–organic framework IRMOF-1 (MOF-5). In a very narrow range of pressures, the adsorbed fluid undergoes a structural and highly cooperative reconstruction and transition between low-density and high-density nanophases, as a result of the competition between the fluid–framework and fluid–fluid interactions. This mechanism evolves with temperature: below 110 K, a reversible stepwise isotherm is observed, which is a result of the bimodal distribution of the coexisting nanophases. This temperature may be considered as a critical temperature of methane confined to nanopores of IRMOF-1. Above 110 K, as the entropy contribution increases, the isotherm shape transforms to a common continuous S-shaped form that is characteristic to a gradual densification of the adsorbed phase as the pressure increases.