Commensurate-incommensurate adsorption and diffusion in ordered crystalline microporous materials.

For homologous series of linear chain molecules, there could be either a match, or mismatch, between the characteristic periodicity of the host structure and the characteristic length of the guest molecules. The major objective of this article is to highlight the influence of commensurateness, or incommensurateness, on both the adsorption and diffusion characteristics. Published experimental data, backed by molecular simulation results, are used to highlight the attendant non-monotonicity in adsorption strengths and diffusivities. We demonstrate the possibility of separating mixtures of n-alkanes, n-alcohols, and hydrocarbon isomers by appropriate and judicious choice of the dimensions, topology, and connectivity of the crystalline host material. Of particular practical interest are entropy-based separations that manifest at pore saturation conditions, relying on differences in the saturation capacities of the constituent species; the exploiting of such entropy effects is discussed with the aid of several examples.