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Ab Initio Investigations of Gas Adsorption on Buckybowls

Burrill, Daniel (2020) Ab Initio Investigations of Gas Adsorption on Buckybowls. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Gas separation processes are prevalent in science and industries to isolate desired or remove undesired gases from mixtures. Of the various methods to perform this separation, surface adsorption has been shown to be a promising avenue due to favorable temperature and pressure limits, high capacity, and chemical tunability. This thesis focuses on using a carbon-based, bowl-like molecule known as a Buckybowl to act as a gas adsorbent. The bowl-like nature of this structure has been shown to have stronger dispersion and electrostatic interactions on the concave side suggesting that it is a potential candidate for gas capture and release systems. In this study, the small gas molecules CH$_4$, CO$_2$, NO, and NO$_2$ are explored computationally as adsorbates on to the Buckybowls corannulene and sumanene as well as the planar structure coronene. It is found that the bowl-up orientation of the Buckybowls, with respect to the adsorbate, has the strongest interaction energy (sumanene CH$_4$, -5.6 kcal/mol) followed by coronene (-2.9 kcal/mol) and then the bowl-down configurations (sumanene CH$_4$, -1.8 kcal/mol). Sumanene was found to have the strongest adsorption energies for these molecules (BU CO$_2$, -6.1 kcal/mol) with binding to corannulene (BU CO$_2$, -4.8 kcal/mol) and coronene (CO$_2$, -3.7 kcal/mol) being weaker. The system studied were also found to exhibit stimulus-induced adsorption/desorption. Specifically, the Buckybowls were found to change selectivity towards specific adsorbates in response to an applied electric field as the interaction energy ordering was altered. Beyond atmospheric molecules, the ability of sumanene to adsorb respiratory irritants was also explored. It was found that for three potent irritants, 2-chlorobenzalmalonitrile, 1,6 hexamethylene diisocyanate, and toluene diisocyanate, the interaction energies are about -14 kcal/mol with attraction largely driven by electrostatic and dispersion effects. No significant energetic barriers due to structural changes were found indicating that sumanene could be a possible gas capture system for these chemical compounds.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Burrill, Danieldjb145@pitt.edudjb145
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee CoChairLambrecht, Daniel
Committee CoChairJordan, Kenneth
Committee MemberFullerton, Susan
Committee MemberStar, Alexander
Date: 8 June 2020
Date Type: Publication
Defense Date: 27 March 2020
Approval Date: 8 June 2020
Submission Date: 15 April 2020
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 92
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Computational Modeling and Simulation
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Buckybowl, sumanene, coronene, corannulene
Date Deposited: 08 Jun 2020 15:52
Last Modified: 08 Jun 2020 15:52


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