| dc.description.abstract | Natural gas is stored as compressed natural gas (CNG) in heavy steel cylinders under pressures of 200-250 atm. However, such a method of storage has certain disadvantages which include multistage compression costs, limited driving range and safety aspects. Hence, alternative methods of storage such as adsorbed natural gas (ANG) which involve adsorbing natural gas at moderate pressures and room temperatures in a suitable nanoporous material are currently being explored. In this thesis, we have isolated model carbon nanostructures and defect geometries most likely to be found in these materials and investigated their specific interactions with methane. The thesis is concerned with ab-initio density functional theory calculations on these various model carbon nanostructures in order to identify the potential candidates that enhance methane adsorption. The adsorption energies of methane on graphite and graphene sheets were similar, with a value of 12.3 kJ/mol for graphene. The Stone-Wales defect in graphene was found to increase the methane adsorption energy to 37.2 kJ/mol, and small surface undulations on the graphene sheet resulted in a smaller increase (16 kJ/mol) in the adsorption energy relative to graphene. The presence of an interstitial carbon was found to significantly reduce the adsorption energy to 5.2 kJ/mol. The enhanced adsorption energy in the case of the Stone-Wales defect was attributed to the significant charge redistribution in the vicinity of the defect. A variety of functional groups such as carboxylic acid (COOH), carbonyl (CO), phenol (OH), pyran (-O-), phenone (=O), peroxide (OOH) and amine (NH2) groups have been observed on carbon surfaces. Extensive density functional calculations of methane adsorbed on various chemically functionalized graphene nanoribbons were carried out to evaluate their methane adsorption energies. A significant finding in this study, is the increased adsorption energies (relative to graphene) that occur for the functional groups containing the OH moiety. The adsorption energies for edge functionalized graphene nanoribbons are 27.6 and 69.7 kJ/mol for COOH and OOH functionalization. Additional computations reveal a strong correlation between the induced dipole moment on methane and the strength of the adsorption energies obtained for the extended nanoribbons. Adsorption isotherms for methane were obtained using grand canonical Monte Carlo simulations for slit-like graphitic pores with and without functional groups. For both OH and COOH functionalized graphite, we observe more than a 40 % increase in the volumetric loading over bare graphite for the highest weight % of the functional group and smallest pore width considered. The maximum volumetric loading decreases with a decrease in the wt% of the functional groups and with an increase in the pore width. | en_US |
