Reminiscent capillarity in subnanopores

Fluids in large and small pores display different behaviors with a crossover described through the concept of critical capillarity. Here we report experimental and simulation data for various siliceous zeolites and adsorbates that show unexpected reminiscent capillarity for such nanoporous materials. For pore sizes D exceeding the fluid molecule size, the filling pressures p are found to follow a generic behavior k B T ln p ∼ γ / ρD where γ and ρ are the fluid surface tension and density. This result is rationalized by showing that the filling chemical potential for such ultra-small pores is the sum of an adsorption energy and a capillary energy that remains meaningful even for severe confinements. A phenomenological model, based on Derjaguin’s formalism to bridge macroscopic and molecular theories for condensation in porous materials, is developed to account for the behavior of fluids confined down to the molecular scale from simple parameters. Confined fluids in porous media exhibit different behaviors in large and small pores, the crossover between the two regimes being not well understood. Here the authors show, by experiments and simulations, that capillarity is reminiscent even for very small pore diameters, providing a unified picture.