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Catalysts 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. / text

In this work samples with silver nanocolumnar structures were successfully fabricated by glancingangle deposition. From SEM investigations of the samples it is concluded that distinct andseparated nanocolumns can be grown without pre-patterned substrates using this method (givensuitable deposition conditions). The sample that exhibits the most distinct and well separatedcolumns was modelled using HFSS with optical properties of silver in nanocolumns obtained bymeasurements on the samples grown by glancing angle deposition, thin enough to not havedeveloped columns. From numerical calculations it was shown that the unit cell arrangement of thecolumns has a large influence on the optical characteristics. It was found that a diamond-like unitcell designed as two identical square lattices shifted by half the lattice spacing in one direction and2-1/2 times the lattice spacing of the other direction gives the best and a fair agreement to theexperimental ellipsometry data. Based on this model calculations were made to determine thewavelength dependent average local current exhibited in the columns as well as the currentdensity. This study showed the occurrence of broadbanded plasmon resonances of longitudinalmode at λ=1363 nm and of transverse mode at λ=545 nm. It was also shown that the opticalcharacteristics are strongly polarization dependent as is expected for such anisotropic samples.

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No description available.

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Although the air-ice interface is atmospherically important, it is difficult to model accurately because exclusion and precipitation of solutes during freezing, deposition of atmospheric species, and heterogeneous/photochemical processes all affect its properties. In this thesis, glancing-angle spectroscopic methods were developed to study ice surfaces. Glancing-angle Raman spectroscopy showed that nitrate is not strongly excluded to the ice surface during freezing, in contradiction with expectations based on equilibrium thermodynamics. Glancing-angle laser-induced fluorescence showed that hydronium ions are not strongly excluded when dilute acidic solutions (HNO3 or HCl) are frozen. These results suggest that solutes are not universally excluded and that care should be taken in modelling surface concentrations on ice. Deposition of HCl(g) was found to result in different pH responses at the "pure" vs. "salty" ice surfaces. Changes at the "salty" ice surface were consistent with the existence of a brine layer at the air-ice interface while changes at the "pure" ice surface were distinctly different, indicating that it may not be appropriate to model it as a cold, liquid layer. Significantly, results also suggest that the sea ice surface is buffered against pH changes, with important implications for interpreting pH-dependent chemistry. The conversion of sea-salt derived halides to reactive halogen species can lead to dramatic changes in the oxidative capacity of the overlying atmosphere. At ambient pH and naturally occurring halide concentrations, the dark ozonation of NaBr and NaI solutions was found to proceed more quickly on frozen vs. aqueous substrates, consistent with a freeze-concentration enhancement in halide concentration at the surface. A photochemical mechanism for halogen release from artificial saline snow was evidenced. The presence of ozone and light in the actinic region leads to accelerated production of Br2 and BrCl and the release of Cl2, in a process enhanced by high surface area, acidity and additional gas phase Br2. The results provide strong evidence for snowpack "halogen explosion" chemistry in which gas phase halogens are recycled back into a concentrated brine layer at the snow grain surface.

Although the air-ice interface is atmospherically important, it is difficult to model accurately because exclusion and precipitation of solutes during freezing, deposition of atmospheric species, and heterogeneous/photochemical processes all affect its properties. In this thesis, glancing-angle spectroscopic methods were developed to study ice surfaces. Glancing-angle Raman spectroscopy showed that nitrate is not strongly excluded to the ice surface during freezing, in contradiction with expectations based on equilibrium thermodynamics. Glancing-angle laser-induced fluorescence showed that hydronium ions are not strongly excluded when dilute acidic solutions (HNO3 or HCl) are frozen. These results suggest that solutes are not universally excluded and that care should be taken in modelling surface concentrations on ice. Deposition of HCl(g) was found to result in different pH responses at the "pure" vs. "salty" ice surfaces. Changes at the "salty" ice surface were consistent with the existence of a brine layer at the air-ice interface while changes at the "pure" ice surface were distinctly different, indicating that it may not be appropriate to model it as a cold, liquid layer. Significantly, results also suggest that the sea ice surface is buffered against pH changes, with important implications for interpreting pH-dependent chemistry. The conversion of sea-salt derived halides to reactive halogen species can lead to dramatic changes in the oxidative capacity of the overlying atmosphere. At ambient pH and naturally occurring halide concentrations, the dark ozonation of NaBr and NaI solutions was found to proceed more quickly on frozen vs. aqueous substrates, consistent with a freeze-concentration enhancement in halide concentration at the surface. A photochemical mechanism for halogen release from artificial saline snow was evidenced. The presence of ozone and light in the actinic region leads to accelerated production of Br2 and BrCl and the release of Cl2, in a process enhanced by high surface area, acidity and additional gas phase Br2. The results provide strong evidence for snowpack "halogen explosion" chemistry in which gas phase halogens are recycled back into a concentrated brine layer at the snow grain surface.

This research investigates an extension of the glancing angle deposition (GLAD) technique and a biosensing application of films produced by GLAD. The extension to GLAD, called phi-sweep (PS), improves column isolation compared to films grown by traditional GLAD (TG) as well as modifies the column tilt angle, , of the slanted columns according to tan(_{PS}) = tan(_{TG}) cos(), where is the sweep angle. The biosensing application makes use of localized surface plasmon resonance in noble metal GLAD films functionalized with rabbit immunoglobulin G (rIgG) to detect binding of anti-rabbit immunoglobulin G (anti-rIgG) to the films' surface. The extinction peak red-shifts a distance dependent on the concentration of anti-rIgG solution in a manner described by the Langmuir isotherm with a saturation value, _{max}, of 29.4 0.7 nm and a surface confined thermodynamic binding constant, K, of (2.7 0.3)10 M. / Microsystems and Nanodevices