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arXiv · 2004.12206

Hysteresis curves reveal the microscopic origin of cooperative CO$_2$ adsorption in diamine-appended metal-organic frameworks

John R. Edison·Rebecca L. Siegelman·Zdenek Preisler·Joyjit Kundu·Jeffrey R. Long·Stephen Whitelam
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Abstract

Diamine-appended metal{organic frameworks (MOFs) of the form Mg2(dobpdc)(diamine)2 adsorb CO2 in a cooperative fashion, exhibiting an abrupt change in CO2 occupancy with pressure or temperature. This change is accompanied by hysteresis. While hysteresis is suggestive of a firstorder phase transition, we show that hysteretic temperature-occupancy curves associated with this material are qualitatively unlike the curves seen in the presence of a phase transition; they are instead consistent with CO2 chain polymerization, within one-dimensional channels in the MOF, in the absence of a phase transition. Our simulations of a microscopic model reproduce this dynamics, and point the way toward rational control, in and out of equilibrium, of cooperative adsorption in this industrially important class of materials.

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John R. Edison, Rebecca L. Siegelman, Zdenek Preisler, Joyjit Kundu, Jeffrey R. Long, Stephen Whitelam. 2020-04-25. Hysteresis curves reveal the microscopic origin of cooperative CO$_2$ adsorption in diamine-appended metal-organic frameworks. https://doi.org/10.1063/5.0054794

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