Investigating cluster formation in adsorption of CO₂,CH₄,and Ar in zeolites and metal organic frameworks at subcritical temperatures

Abstract

The critical temperatures, T_c, of CO₂, CH₄, and Ar are 304 κ, 191 κ, and 151 κ, respectively. This paper highlights some unusual characteristics of adsorption and diffusion of these molecules in microporous structures such as zeolites and metal organic frameworks at temperatures T < T_c. Published experimental adsorption data for T < T_c show that the isotherms invariably display stepped characteristics. The inverse thermodynamic factor 1/Γ_i = d ln c_i/d ln f_i exceeds unity for a range of fugacities f_i and molar concentrations ci within the pore corresponding to the steep portion of the isotherm. With the aid of Monte Carlo simulations of isotherms for different temperatures T < T_c in a variety of zeolites (AFI, MTW, FAU, NaY, MFI, and MOR), metal-organic frameworks (IRMOF-1, CuBTC, MIL-47 (V), and MIL-53 (Cr)), and covalent-organic frameworks (COF-102, and COF-108), we investigate the conditions required for 1/Γ_i> 1. For each of the three species investigated, data on pore concentrations c_i at any given temperature below T_c fall within the binodal region for the bulk fluid phase. We present evidence to suggest that, in the concentration ranges for which 1/Γ_i> 1, clustering of molecules occurs. The extent of clustering is enhanced as T falls increasingly below T_c. Furthermore, molecular dynamics simulations of diffusion demonstrate that the concentration dependence of the diffusivities is markedly influenced in the regions where 1/Γ_i> 1. In regions where molecular clustering occurs, the Fick diffusivity shows, in some cases, a decreasing trend with concentration.