Computer simulation of ethylene glycol oxidation and methanol – water interactions

Lee, Christopher 2013. Computer simulation of ethylene glycol oxidation and methanol – water interactions. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

In this project, density functional theory calculations were performed to study the adsorption of ethylene glycol to the MgO (100), MgO (130), Al2O3 (0001), PdO (101) surfaces, as well as Au38 and Au38O16 nanoparticles. Adsorption of ethylene glycol is favourable to all of these surfaces with Al2O3 (0001) and PdO (101) showing the most favourable adsorption at -168 kJ mol-1 and -135 kJ mol-1 respectively. The MgO surfaces showed adsorption energies between -80 kJ mol-1 and -100 kJ mol-1, and the gold nanoparticles showed lower adsorption energies at approximately -35 kJ mol-1. Barriers to O-H activation and C-H activation of ethylene glycol were also studied on these surfaces. The barriers to O-H activation were small over each of the surfaces (between 8 and 46 kJ mol-1) and large for the gold nanoparticles (108 kJ mol-1). The barriers to C-H activation were very large over the MgO surfaces (>300 kJ mol-1), and lower over the PdO (101) surface (63 kJ mol-1) and the gold nanoparticles (68 kJ mol-1). C-H activation was found to not be possible over the Al2O3 (0001) surface. Classical molecular dynamics studies were performed on various water and methanol mixtures as well as in the presence of a hydroxylated Al2O3 (0001) surface. It was found that in methanol there are on average 1.1 oxygen – oxygen close contacts with other methanol molecules in pure methanol, and water has on average between 2.03 and 2.86 oxygen – oxygen close contacts, with more being present at higher temperatures. The presence of a hydroxylated aluminium oxide surface induces local ordering in the methanol molecules resulting in an increase in methanol – methanol and water – methanol oxygen – oxygen contacts, however there is a decrease in water oxygen – water oxygen contacts.

Item Type:	Thesis (PhD)
Status:	Unpublished
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Date of First Compliant Deposit:	30 March 2016
Last Modified:	19 Mar 2016 23:25
URI:	https://orca.cardiff.ac.uk/id/eprint/51368

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