Methods for modifying the physical and catalytic properties of surfaces

textCatalysts can be significantly improved by modifying their structure or composition. Simple adaptations of the physical structure of a catalyst can give rise to changes in the chemical behavior, in part, due to alterations in the coordination of active sites. Modifications in the surface or bulk composition of a material have a profound impact on the chemistry that is promoted as a result of electronic and physical factors. Optimizing these qualities may enhance the catalyst’s activity, selectivity or stability. In this dissertation, we explore the application of two distinct approaches for modifying the chemical properties of catalytically active materials. Through the use of a broad array of techniques we quantify changes in critical properties such as physical-crystallographic structure; morphology, surface area and porosity; as well as catalytic activity, selectivity and stability. First, reactive ballistic deposition of metal atoms within a low pressure gas provides a unique opportunity for synthesizing thin films of a wide variety of materials. The morphology, structure, and porosity of the resulting material can be tailored through control of the deposition angle and substrate temperature. By conducting deposition perpendicular to the surface, a film can be grown with a dense, conformal structure. On the other hand, deposition at oblique angles results in high surface area, porous films comprised of regular arrays of nanocolumnar structures. Furthermore, variations in the deposition angle allow for the inclusion of under-coordinated sites which change the chemical activity of the surface. Improvements in the activity, selectivity and stability of transition metal catalysts can be made by alloying the catalyst with a second element. The formation of molybdenum carbide decreases the strength of chemisorption on the surface, with respect to molybdenum, and improves selectivity for the dehydrogenation of formic acid. Platinum is active for the water-gas shift reaction. However, this catalyst cannot operate at low temperatures due to CO poisoning and is susceptible to deactivation due to accumulation of carbonaceous deposits. The formation of a platinum-copper near-surface alloy dramatically modifies the interactions of the surface with CO, H₂O and H₂ which can enhance the performance of this catalyst for the water-gas shift reaction.Chemical Engineerin