Date of Award

Summer 7-17-2014

Document Type


Degree Name

Doctor of Philosophy (PhD)

First Advisor

J. Will Medlin

Second Advisor

John L. Falconer

Third Advisor

Daniel K. Schwartz


In this thesis, we present an investigation, starting from surface science experiments, leading to design of supported catalysts, of how adsorption orientation can be used to affect reaction selectivity of highly functional molecules.

The surface chemistry of furfuryl alcohol and benzyl alcohol and their respective aldehydes was studied on a Pd(111) single-crystal surface under ultra-high vacuum conditions. Temperature-programmed desorption experiments showed that synergistic chemistry existed between the aromatic ring and the oxygen-containing functional group, each allowing the other to participate in reaction pathways that a monofunctional molecule could not. Most important of these was a deoxygenation reaction that occurred more readily when the surface was crowded by the highest exposures. High-resolution electron energy loss spectroscopy revealed that at these high exposures, molecules were oriented upright on the surface, with the aromatic function extending into vacuum. In contrast, at low exposures, molecules were oriented flat on the surface. The upright adsorption geometry was correlated with deoxygenation, whereas the flat-lying geometry was correlated with decarbonylation.

The insight gained from surface science experiments was utilized in catalyst design. Self-assembled monolayers of alkanethiolates were used to systematically reduce the average surface ensemble size, and the reaction selectivity was tracked. When a sparsely-packed monolayer was used, such as one formed by 1-adamantanethiol, the reactant furfural was still able to lie flat on the surface and the reaction selectivity was similar to that of the uncoated catalyst. However, when a densely-packed monolayer, formed by 1-octadecanethiol, was used, furfural was not able to adsorb flat on the surface and instead adopted an upright conformation, leading to a drastic increase in aldehyde hydrogenation and hydrodeoxygenation reaction selectivity. Using an even higher sulfur coverage from a monolayer formed by 1,2-benzenedithiol, we determined that hydrodeoxygenation selectively occurred on catalyst particle steps and edges from an upright structure, whereas decarbonylation occurred on particle terraces from a flat-lying structure.

Control of furfural adsorption orientation was also achieved through the use of NiCu bimetallic catalysts. The aromatic furan ring was repelled from surface Cu, leading to an upright structure. However, under hydrogenation conditions, Ni tended to be near the surface of thin films and catalysts, leading to less dramatic selectivity enhancement. The presence of a 1-octadecanethiol monolayer kinetically stabilized the surface termination, allowing Cu to remain at the surface.