(395ab) Predicting CO2 Adsorption in Polymers of Intrinsic Microporosity

Polymers of Intrinsic Microporosity (PIMs) are a novel class of ultra-rigid, glassy polymers that due to their contorted structure pack inefficiently, which creates accessible free volume. The size scale of this inherent free volume (< 0.7 nm) in combination with the ability of chemical functionalization of the polymer backbone gives this class of materials great potential for carbon dioxide storage and separation. The quality of any material at adsorbing a gas relies heavily on, and is dictated by, the amount of pore volume present and the energy of interactions with the pore wall. Both of these characteristics need to be understood and maximized if PIMs are to be realized as a carbon dioxide sequestration material. Atomistic molecular simulations offer unique insight into understanding the adsorption phenomena in a way that complements experiments, which facilitates a full understanding of the material’s adsorbing capacity.  The work presented here show predictive molecular simulations of both low and high pressure carbon dioxide adsorption of PIM-1, which compare well with available experimental data. In addition, several chemical and structural functionalizations were made to PIM-1 to determine the resulting effect on carbon dioxide adsorption as a means to increase both the enthalpy of adsorption and the total adsorbing capacity of linear polymers of intrinsic microporosity.