Graduation Year


Document Type




Degree Name

Doctor of Philosophy (Ph.D.)



Degree Granting Department


Major Professor

Brian Space, Ph.D.

Committee Member

Randy W. Larsen, Ph.D.

Committee Member

Henry Lee Woodcock, Ph.D.

Committee Member

Wayne C. Guida, Ph.D.


CO2 separation, computer simulation, grand canonical Monte Carlo, hydrogen storage, metal-organic frameworks, statistical mechanics


Metal--organic frameworks (MOFs) are porous crystalline materials that are synthesized from rigid organic ligands and metal-containing clusters. They are highly tunable as a number of different structures can be made by simply changing the organic ligand and/or metal ion. MOFs are a promising class of materials for many energy-related applications, including H2 storage and CO2 capture and sequestration. Computational studies can provide insights into MOFs and the mechanism of gas sorption and separation. Theoretical studies on existing MOFs are performed to determine what structural characteristics leads to favorable gas sorption mechanisms. The results from these studies can provide insights into designing new MOFs that are tailored for specific applications. In this work, grand canonical Monte Carlo (GCMC) simulations were performed in various MOFs to understand the gas sorption mechanisms and identify the favorable sorption sites in the respective materials. Experimental observables such as sorption isotherms and associated isosteric heat of adsorption, Qst, values can be generated using this method. Outstanding agreement with experimental measurements engenders confidence in a variety of molecular level predictions. Explicit many-body polarization effects were shown to be important for the modeling of gas sorption in highly charged/polar MOFs that contain open-metal sites. Indeed, this was demonstrated through a series of simulation studies in various MOFs with rht topology that contain such sites. Specifically, the inclusion of many-body polarization interactions was essential to reproduce the experimentally observed sorption isotherms and Qst values and capture the binding of sorbate molecules onto the open-metal sites in these MOFs. This work also presents computational studies on a family of pillared square grid that are water-stable and display high CO2 sorption and selectivity. These MOFs are deemed promising for industrial applications and CO2 separations. Simulations in these materials revealed favorable interactions between the CO2 molecules and the SiF62- pillars. Further, the compound with the smallest pore size exhibits the highest selectivity for CO2 as demonstrated through both experimental and theoretical studies. Many other MOFs with intriguing sorption properties are investigated in this work and their sorption mechanisms have been discerned through molecular simulation.

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