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Issue 31, 2017
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Commensurate–incommensurate adsorption and diffusion in ordered crystalline microporous materials

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Abstract

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.

Graphical abstract: Commensurate–incommensurate adsorption and diffusion in ordered crystalline microporous materials

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Supplementary files

Article information


Submitted
18 Jun 2017
Accepted
25 Jul 2017
First published
25 Jul 2017

Phys. Chem. Chem. Phys., 2017,19, 20320-20337
Article type
Perspective

Commensurate–incommensurate adsorption and diffusion in ordered crystalline microporous materials

R. Krishna and J. M. van Baten, Phys. Chem. Chem. Phys., 2017, 19, 20320 DOI: 10.1039/C7CP04101B

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