UC Berkeley

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 first-order 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, providing a physical understanding of cooperative adsorption in this industrially important class of materials.