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Synthesis and characterization of nanostructured palladium-based alloy electrocatalystsSarkar, Arindam 22 October 2009 (has links)
Low temperature fuel cells like proton exchange membrane fuel cells (PEMFC) are expected to play a crucial role in the future hydrogen economy, especially for transportation applications. These electrochemical devices offer significantly higher efficiency compared to conventional heat engines. However, use of exotic and expensive platinum as the electrocatalyst poses serious problems for commercial viability. In this regard, there is an urgent need to develop low-platinum or non-platinum electrocatalysts with electrocatalytic activity for the oxygen reduction reaction (ORR) superior or comparable to that of platinum.
This dissertation first investigates non-platinum, palladium-based alloy electrocatalysts for ORR. Particularly, Pd-M (M = Mo and W) alloys are synthesized by a novel thermal decomposition of organo-metallic precursors. The carbon-supported Pd-M (M = Mo, W) electrocatalyts are then heat treated up to 900 oC in H2 atmosphere and investigated for their phase behavior. Cyclic voltammetry (CV) and rotating disk electrode (RDE) measurements reveal that the alloying of Pd with Mo or W significantly enhances the catalytic activity for ORR as well as the stability (durability) of the electrocatalysts. Additionally, both the alloy systems exhibit high tolerance to methanol, which is particularly advantageous for direct methanol fuel cells (DMFC).
The dissertation then focuses on one-pot synthesis of carbon-supported multi-metallic Pt-Pd-Co nanoalloys by a rapid microwave-assisted solvothermal (MW-ST) method. The multi-metallic alloy compositions synthesized by the MW-ST method show much higher catalytic activity for ORR compared to their counterparts synthesized by the conventional borohydride reduction method. Additionally, a series of Pt encapsulated Pd-Co nanoparticle electrocatalysts are synthesized by the MW-ST method and characterized to understand their phase behavior, surface composition, and electrocatalytic activity for ORR.
Finally, the dissertation focuses on carbon-supported binary Pt@Cu and ternary PtxPd1-x@Cu “core-shell” nanoparticles synthesized by a novel galvanic displacement of Cu by Pt4+ and Pd2+ at ambient conditions. Structural characterizations suggest that the Pt@Cu nanoparticles have a Pt-Cu alloy layer sandwiched between a copper core and a Pt shell. The electrochemical data clearly point to an enhancement in the activity for ORR for the Pt@Cu “core-shell” nanoparticle electrocatalysts compared to the commercial Pt electrocatalyst, both on per unit mass of Pt and per unit active surface area basis. The increase in activity for ORR is ascribed to electronic modification of the outer Pt shell by the Pt-Cu alloy core. However, incorporation of Pd to obtain PtxPd1-x@Cu deteriorates the activity for ORR. / text
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Synthesis and characterization of undoped and Ag doped TiO2, ZnO and ZnS nanoparticles for the photocatalytic degradation of 2-chlorophenol under UV irradiation.Onkani, Shirley Priscilla 08 July 2019 (has links)
M.Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Phenol, 2-chlorophenol (2-CP) is used in the manufacture of several chemical compounds including other chlorophenols, dyes, dentifrice and pesticides. The usage of these chemicals results in the discharge of 2-CP that is harmful to most biota in the environment. Therefore there is need to remove or degrade 2-CP from the environment, especially in water. This research focused on the synthesis, characterization and application of Ag doped semiconductor (TiO2, ZnO, and ZnS) nanoparticles for the removal of 2-CP from water. Sol-gel and co-precipitation methods were used to synthesize the nanoparticles with different Ag contents (1%, 3% and 5%). Silver metal was used as a doping agent due to its antibacterial activity and ability to improve the photocatalytic activity of the semiconductors for 2-CPdegradation under UV irradiation. Characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR), Ultra-violet visible spectroscopy (UV-Vis) and photoluminescence spectra (PL) were used to characterize the structural, optical and physical properties of the nanoparticles, while Transmission electron microscopy (TEM) was used to characterize the surface of the nanoparticles. The XRD results confirmed the formation of anatase, wurtzite and blend phases of TiO2, ZnO and ZnS nanoparticles, respectively. The band gaps of the synthesized nanoparticles were 3.42 eV, 3.23 eV and 3.12 eV for TiO2, ZnO and ZnS nanoparticles respectively. The TEM images showed that all synthesized nanoparticles were uniform in shape. Photocatalytic degradation of 2-CP under UV irradiation confirmed that the semiconductor’s photocatalytic activities improved with the addition of Ag ions. The best removal percentage was obtained at doped Ag percentages of 5, 1 and 5 % using TiO2, ZnO and ZnS, respectively. In addition, the effects of various parameters affecting the photocatalytic degradation such as pH, initial concentrations of 2-CP and amount of catalyst (Ag doped TiO2, ZnO and ZnS, respectively) loading were examined and optimized. At the different initial concentrations of 2-CP, namely, 8, 20 and 50 ppm, the highest degradation efficiency was obtained at pH of 10.5 and 5 mg of catalyst dosage. However a decrease in initial concentration of 2-CP showed an increase in the photocatalytic efficiency. The degradation percentage of 2-CP obtained with Ag doped TiO2; ZnO and ZnS nanoparticles were 74.74, 57.8 and 45.49 %, respectively. Doping of these materials with Ag enhanced their photocatalytic activity; thus, they have the potential of degrading phenolic compounds, especially 2-chlorophenol, in water.
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