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Metal nanoparticles have a large surface area to volume ratio compared to their bulk counterparts, which makes them attractive to use as catalysts. Atoms on the surface of metal nanoparticles are very active due to their high surface energy resulting from their unsatisfied valency. First synthesis of gold nanoparticles with different shapes and bimetallic structure are explored in detail. Then an experimental method which could distinguish between the two mechanisms (homogeneous or heterogeneous) by using hollow plasmonic gold nanocatalyst is developed. Furthermore the catalytic activity of gold nanocages was changed by adding an inner platinum or palladium nanoshell. Results suggested that adding palladium inner shell increased the activity of gold nanocages towards the reduction nitro groups to amino groups. Controlling the selectivity of the catalyst is an important goal of catalysis research. Lastly selectivity of the plasmonic nanocatalyst (Gold sphere-Gold shell Nanorattles) with multiple plasmon modes was studied for photo-dimerization of nitro groups into azo dimers were studied on gold nanocatalyst surface. Results showed that selectivity can be controlled by changing the wavelength of the light exciting surface plasmon.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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Rest potential measurements, cyclic voltammetry, linear sweep voltammetry and constant potential coulometry were used to determine the electrochemical response of arsenopyrite in the absence and in the presence of cyanide and to determine its dissolution chemistry. Surface oxidation of arsenopyrite is proposed to proceed by a two-step reaction sequence. FeOOH, H₂AsO₃⁻, and Sᵒ, are produced in the initial step. Oxidation of Sᵒ to SO₄²⁻, and H₂AsO₃⁻ to HAsO₄²⁻ account for the second step. Coulometric results confirmed that 14 electrons are involved in the overall reaction. The implications of these results on the cyanidation of arsenical gold-bearing concentrates were also investigated. The response of four different concentrates to various cyanidation techniques was examined. Alkaline pressure oxidation in 1 M NaOH, at 200°C and under 500 psi of oxygen overpressure followed by conventional cyanidation resulted in 81% gold extraction from a concentrate that yielded only 2% gold extraction after direct cyanidation.

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