Temperature Programmed Desorption and Infrared Spectroscopic Studies of Interfacial Hydrogen Bonds for Small Molecules Adsorbed on Silica and Within Metal Organic Frameworks
Abelard, Joshua Erold Robert
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Hydrogen bonds are arguably the most important reversible intermolecular forces. However, surprisingly few studies of their fundamental nature at the gas-surface interface have been performed. Our research investigated sulfur mustard (HD) adsorption by characterizing interfacial hydrogen bonding and dispersion forces for the simulant molecules 2-chloroethyl ethyl sulfide (2-CEES) and methyl salicylate on well-characterized hydroxyl-functionalized surfaces (silica and UiO-66). Our approach utilized infrared spectroscopy to study specific surface-molecule interactions and temperature-programmed desorption to measure activation energies of desorption. 2-CEES has two polar functional groups, the chloro and thioether moieties, available to accept hydrogen bonds from free surface silanol groups. Diethyl sulfide and chlorobutane were investigated to independently assess the roles of the chloro and thioester moieties in the overall adsorption mechanism and to explore the interplay between the charge transfer and electrostatic contributions to total hydrogen bond strength. The results indicate that both SiOH---Cl and SiOH---S hydrogen bonds form when 2-CEES adsorbs to silica or hydroxylated UiO-66. However, a more stable configuration in which both polar groups interact simultaneously with adjacent silanol groups likely does not form. A systemaic study of chloroalkanes revealed that dispersion forces involving the methylene units in 2-CEES contribute to nearly half of the total activation energy for desorption from silica. Methyl salicylate possesses aromatic, hydroxyl, and ester functional groups, each of which is a potential hydrogen bond acceptor. We found that uptake on silica is mainly driven by the formation of carbonyl-silanol and hydroxyl-silanol hydrogen bonds with additional contributions from weaker interactions. In an effort to learn more about the SiOH---π bond, the adsorption of simple substituted benzene derivatives on silica was investigated to probe the effects of electron withdrawing and donating substituents. Results indicate that the substituted benzene derivatives adsorb to silica via a cooperative effect involving SiOH---π hydrogen bonds and additional substituent-surface interactions. The strength of the SiOH---π bond is enhanced by electron donating groups and weakened by electron withdrawing groups.
- Doctoral Dissertations