Density functional theories and molecular simulations of adsorption and phase transitions in nanopores.

Abstract

The nonlocal density functional theory (NLDFT) of confined fluids is tested against Monte Carlo simulations by using the example of Lennard-Jones (LJ) fluid sorption in slit-shaped and cylindrical nanopores ranging from 0.3 to 10 nm in width. The fluid-fluid and solid-fluid parameters of the LJ potentials were chosen to represent several experimentally important adsorption systems: nitrogen and carbon dioxide in activated carbons, zeolites, and mesoporous molecular sieves of the MCM-41 type. Freezing in nanopores is discussed using the example of methane sorption in carbon at 111 K. Comparison with reference experiments is given when available. Two versions of NLDFT, the smoothed density approximation and the fundamental measure theory, are considered. It is shown that NLDFT approaches with properly chosen parameters provide quantitative agreement with the results of Monte Carlo simulations and reference experiments. Appreciable deviations are found in extremely narrow pores of less than two molecular diameters in width. In wider pores, NLDFT models can be used for quantitative predictions of reversible and hysteretic adsorption isotherms and analyses of the specifics of phase transformations, including the equilibrium and spinodal phase transitions.