The development of highly selective and active, long-lasting, robust, low-cost and environmentally benign catalytic materials is the greatest challenge in the area of catalysis study. In this context, core-shell structures where the active sites are embedded inside the protecting shell have attracted a lot of researchers working in the field of catalysis owing to their enhanced physical and chemical properties suppress catalyst deactivation. Also, a new active site generated at the interface between the core and shell may increases the activity and efficiency of the catalyst in catalytic reactions especially for oxide shells that exhibit redox properties such as TiO2 and CeO2. Moreover, coating oxide layer over metal nanoparticles (NPs) can be designed to provide porosity (micropore/mesopore) that gives selectivity of the various reactants by the different gas diffusion rates. In this thesis, we will discuss the concept of catalyst stabilization against metal sintering by a core-shell system. In particular we will study the mechanistic of forming core-shell particles and the key parameters that can influence the properties and morphology of the Pt metal particle core and SiO2 shell (Pt@SiO2) using the reverse micro-emulsion method. The Pt@SiO2 core-shell catalysts were investigated for low-temperature CO oxidation reaction. The study was further extended to other catalytic applications by varying the composition of the core as well as the chemical nature of the shell material. The Pt NPs were embedded within another oxide matrix such as ZrO2 and TiO2 for CO oxidation reaction. These materials were studied in details to identify the factors governing the coating of the oxide around the metal NPs. Next, a more challenging system, namely, bimetallic Ni9Pt NPs embedded in TiO2 and ZrO2 matrix were investigated for dry reforming of methane reaction at high temperatures. The challenges of designing Ni9Pt@oxide core-shell structure with TiO2 and ZrO2 and their tolerance of the structure to the conditions of dry reforming of methane will be discussed.

In this study, the wastewater generated from etching process of the Printed Circuit Board (PCB) was treated by a process including both acidification and coagulation/sedimentation and then followed by the catalytic wet air oxidation (CWAO) over different catalysts (either Pt/SiO2¡PAl2O3 or Pt¡PX/£^-Al2O3) process in series. Although the initial chemical oxygen demand (COD) concentration of the wastewater is as high as 7740-12700 mg/L, the effluent of the pretreatment process was measured to have COD value in ranges of 3050-4260 mg/L. Several re-action parameters, such as reaction temperatures (200-260¢J), oxygen partial pressures (0-3 MPa), and two kinds of catalysts were performed experimentally to investigate the COD reduction of the wastewater during the CWAO process. Both reaction temperature and variety of catalyst are found most effectively on the COD reduction. However, the effect of oxygen partial pressure on the COD reduction is just in little. Results showed that the COD reduction during the CWAO over the Pt¡PX/£^-Al2O3 catalyst process is the most significant, which with a tow-step re-action and both the two reactions do obey first-order reaction kinetics. A change from a higher reaction activity of the CWAO reaction to a slower one implies a decrease of the reaction rate. On basis of our experiments data, the effective operating conditions of CWAO for the COD reduction was observed to be at temperature of 260¢J under oxygen partial pressure of 2.0 MPa and at a retention time period of 60 min. The COD conversion was calculated as high as 75%; however, it could be enhanced up to 78% and 91%, respectively, when the CWAO was conducted in presence of the Pt/SiO2¡PAl2O3 and Pt¡PX/£^-Al2O3 catalysts, respectively. It can be seen that the organic compound of the wastewater was mineralized most completely (with a COD/TOC ratio of 3.7¡Ó0.2) after the CWAO over the Pt¡PX/£^-Al2O3 catalyst process. Furthermore, a higher COD/TOC ratio of 3.9¡Ó0.3 was achieved when the Pt/SiO2¡PAl2O3 catalyst was in presence of the CWAO process, and the primitive WAO process had the highest COD/TOC ratio of 4.8¡Ó0.4. The experimental data showed that both a higher reaction temperature (¡Ù260¢J) and an application of catalyst are more important factors for the min-eralization of the organic compound of the wastewater during the CWAO process. In our investigation, BOD5/COD ratio has been used to assess if the WAO and/or the CWAO process treatment yield products more amenable to biodegradation. The BOD5/COD ratio was 0.68-0.93 when the reaction temperature was above 220¢J and the retention time was as long as 60 min. Unfortunately, the BOD5/COD ratio of the effluent from the CWAO process came out a lower value (0.45-0.65) though it was under the same reaction conditions. It is probable that the biodegradable portion of the organic compounds of the wastewater were decomposed easier during the CWAO process than during the WAO process. In addition, it was found that the products of the wastewater was decomposed partially into CO2 and into some low molecular weigh acids, such as formic acid, acetic acid, propionic acid, etc. The activation energy with respect to COD was calculated to be 38.42 kJ/mole and 83 kJ/mole, respectively, for the first-step reaction and for the second-step reaction, respectively, of the WAO process. It was al-so calculated that the first-step reaction of the CWAO over the Pt/SiO2¡PAl2O3 catalyst process has activation energy of 18.25 kJ/mole and 25.76 kJ/mole is for the second-step reaction. However, 16.05 kJ/mole and 49.61 kJ/mole are calculated for the first-step and the sec-ond-step reactions, respectively, of the CWAO over the Pt¡PX/£^-Al2O3 catalyst process. It can be seen that the application of both the Pt/SiO2¡PAl2O3 and the Pt¡PX/£^-Al2O3 catalysts has a significant effect on reducing the activation energy of the WAO. It was observed that the total COD conversion of the wastewater is as high as 96% and the BOD5/COD ratio of the effluent has been en-hanced up to more than 0.6. The combination of both the CWAO over the Pt¡PX/£^-Al2O3 catalyst and the biological treatment is a promising tech-nique for the PCB¡¦s wastewater treatment to fit the wastewater control regulation in Taiwan, which requests the COD value of the wastewater discharged should be less than 120 mg/L.

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.