Innovative Gas Separations For Carbon Capture: A Molecular Simulation Study

UoM administered thesis: Phd


Adverse changes in the Earth's climate are thought to be due to the output of carbon dioxide from power stations. This has led to the development of many new materials to remove CO2 from these gas streams. Polymers of intrinsic microporosity (PIMs) are a novel class of polymers that are rigid with sites of contortion. These properties result in inefficient packing and so lead to large pore volumes and high surface areas. The inclusion of Tröger's base, a contortion site made up of two nitrogen atoms, is thought to lead to increased uptake of CO2. The combination of electrostatic interactions with strong van der Waals forces should interact favourable with the quadrupole moment of CO2.Here a molecular simulation study of a selection of these polymers is presented. The study begins by developing a quick screening method on single polymer chains. This shows that the high surface area and adsorption affinity are a result of the contorted nature of PIMs along with the inclusion of groups such as Tröger's base.The creation of atomistic models that reproduce the space packing ability of these polymers is also explored. Methods developed for PIMs in literature are investigated along with a new method developed during this study. GCMC simulations are then used to investigate the adsorption of CO2. In this study it is seen that that these polymers possess a well percolated network of both ultramicropores and supermicropores with a significant fraction of these pores being close to the kinetic diameter of CO 2. It is posited that these pores may be the result of the inclusion of Tröger's base. It is also shown that this produces a particularly favourable site for adsorption. The phenomenon of swelling as a result of CO2 adsorption is also investigated using a variety of methods that make use of the output from the GCMC simulations. It was found that swelling is negligible for pressures of up to 1 bar. This result is important as swelling in the polymer can lead to a reduction in selectivity and an increase in permeability, which can affect the overall material's performance.


Original languageEnglish
Awarding Institution
Award date31 Dec 2013