Review and analysis of molecular simulations of methane, hydrogen, and acetylene storage in metal-organic frameworks.
2013 ii Dedication This doctorate research work is dedicated to God, My wife Mary and my sons (Joshua and John). iii Acknowledgments First I would like to thank my supervisor, Dr. Andrew J. Goudy for giving me the scientific freedom during the work on my thesis. Also, for his great support and constructive criticism. I will also like to thank all the members of the hydrogen storage group for a great time with them and friendly working atmosphere: Dr. I am also grateful to the entire staff and faculty of the Department of Chemistry for making the learning environment friendly. To my committee members, I say thank you. I must say a big thank you to my parents Presiding Elder and Deaconess Amos Orefuwa and my siblings, Daniel, Esther, Dupe, Tope and Elizabeth for their prayers, and encouragement. To my wife, without a flinch of a doubt, you and the boys are highly appreciated. You gave me all the time, support and prayers that I needed and sacrificed a lot for me. Thank you my wife, Mary, and the boys, John and Joshua. ABSTRACT The synthesis, functionalization and scaffolding potentials of MOFs for improving H 2 , CH 4 and CO 2 storage are hereby reported. A rapid and inexpensive solvothermal method for producing high quality IRMOF-8 (isoreticular metal–organic framework) crystals in 2–4 hours has been developed. This is 10-12 times faster than the traditional solvothermal convective oven synthesis method. The effect of temperature on the pore volume, pore size, specific surface area(SSA) and hydrogen storage capacity of convective oven synthesized IRMOF-8 (C-IRMOF-8) and the rapid solvothermal synthesized IRMOF-8 (RS-IRMOF-8) were also investigated. The optimum synthesis temperatures were 120 o C and 155 o C for C-IRMOF-8 and RS-IRMOF-8, respectively. BET analysis showed that the SSA and pore volume of RS-IRMOF-8 (1801 m 2 /g, 0.693 cm 3 /g) were greater than that of C-IRMOF-8(1694 m 2 /g, 0.603 cm 3 /g) at the optimum temperatures. In a further study, a novel IRMOF-8-NO 2 was synthesized. BET and gas sorption analysis showed that a large decrease in surface area and pore volume of the IRMOF-8-NO 2 did not result in a proportionate decrease in gas sorption capability. The amounts of hydrogen, methane and carbon dioxide adsorbed by the IRMOF-8-NO 2 were disproportionately high. A new concept known as sticking factor was determined for the adsorption of each gas on the …