Fundamental understanding of molecular interactions and transport within microporous materials displaying cooperative Type V adsorption is challenged by the unique features of this isotherm type. In order to capture a broad understanding of this uncommon, yet industrially relevant, behavior in microporous materials, this investigation examines the adsorption equilibria and kinetics of methanol and ethanol in both a metal-organic framework (MOF) material, ZIF-8, and a high free volume polymer of intrinsic microporosity, poly[1-(trimethylsilyl)-1-propyne] (PTMSP). A novel formulation that can capture the cooperative effects of small alcohols in its description of adsorption equilibria and kinetics is proposed. It is subsequently applied to successfully capture some previously uncharacterized or semiempirically characterized data for equilibria and the loading dependence of the diffusivity in both ZIF-8 and PTMSP, which are materials chosen for their industrial relevance. Finally, it is anticipated that the results of this study can fill the current void that exists in meaningful mechanistic and analytical descriptions of cooperative equilibrium and diffusion phenomena in microporous materials.
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