A New Statistical Theory for Constructing Sorption Isotherms in Mesoporous Structures Represented by Bethe Lattices.

Abstract

In the present work, a new statistical theory is developed to describe adsorption and desorption in mesoporous materials (pore sizes ranging from 2 to 50 nm) represented by pore networks in the form of Bethe lattices. The new theory is an extension of a previous theory applied for Statistically Disordered Chain Model (SDCM) structures and incorporates the cooperative effects emerging during phase transitions in pore networks. The theory is validated against simulations and algorithmic models that describe sorption of lattice and real fluids in Bethe lattices. It is seen that the pore network coordination number, or pore connectivity, z, has a significant impact on two important processes observed in pore networks: pore assisting condensation during adsorption and evaporation by percolation during desorption. The inclusion of pore connectivity in the earlier developed framework accounting for cooperativity effects is an important step, rendering the existing models to mimic fluid behavior in real materials more accurately. Hence, the new theory inherently contains all essential elements that may offer the extraction of more reliable pore size distributions utilizing both the adsorption and desorption branches of the isotherm.