Synthesis and characterization of pt-sn/c cathode catalysts via polyol reduction method for use in direct methanol fuel cell

Philosophiae Doctor - PhDDirect methanol fuel cells (DMFCs) are attractive power sources as they offer high conversion efficiencies with low or no pollution. One of the major advantages DMFCs has over PEMFCs is that methanol is a liquid and can be easily stored where in the case for PEMFCs storing hydrogen requires high pressures and low temperatures. However, several challenging factors especially the sluggish oxygen reduction reaction (ORR) and the high cost of Pt catalysts, prolong their commercialization. With the aim to search for more active, less expensive more active ORR catalysts and methanol tolerant catalysts than pure Pt, this dissertation focuses on the development of low loading Pt electrocatalyst and the understanding of their physical and electrochemical properties. Pt-Sn/C electrocatalsyts have been synthesized by a modified polyol reduction method. The effect of temperature, pH, water, sonication and addition of carbon form were studied before a standard polyol method was established. From XRD patterns, the Pt-Sn/C peaks shifted slightly to lower 2Ө angles when compared with commercial Pt/C catalyst, suggesting that Sn is alloying with Pt. Based on HRTEM data, the Pt-Sn/C nanoparticles showed small particle sizes well-dispersed onto the carbon support with a narrow particle distribution. The particle sizes of the different as-prepared catalysts were found to be between 2-5 nm. The Pt-Sn/C HA Slurry pH3 catalysts was found to be the best asprepared catalyst and was subjected to heat-treatment in a reducing atmosphere at 250-600 °C which led to agglomeration yielding nanoparticles of between 5-10 nm. The Methanol Oxidation Reaction (MOR) on the as-prepared Pt-Sn/C HA Slurry pH3 catalyst appeared at lower currents (+7.11 mA at 860 mV vs. NHE) compared to the commercial Pt/C (+8.25 mA at +860 mV vs. NHE) suggesting that the Pt-Sn/C catalyst has „methanol tolerance capabilities‟. Pt-Sn/C HA Slurry pH3 and Pt-Sn/C 250 °C catalysts showed better activity towards the ORR than commercial Pt/C with specific and mass activities higher than Pt/C at +0.85 V vs NHE. The Tafel slopes of Pt-Sn/C HA Slurry pH3 catalyst was -62 and -122 mV dec-1 for the low and high current regions respectively and suggests that the ORR mechanism is similar to that of commercial Pt/C indicating that the ORR kinetics was not negatively influenced by the addition of tin. It was found that the electrochemical oxidation reduction reaction follows first order kinetics of a multi-electronic (n=4ē) charge transfer process producing water. All the Pt-Sn/C catalysts showed resistance towards MOR and it was found for the heat-treated catalysts that an increase in temperature resulted in an increase in methanol tolerance. The synthesized Pt-Sn/C HA Slurry pH3 catalysts were also tested in a fuel cell environment. Electrodes were prepared by either spraying on Toray carbon paper with the Asymtek machine or by VI spraying directly on the membrane with a hand spray gun the catalysts coated membrane (CCM) technique. Polarization curves obtained in DMFC with CCM showed superior performance than electrode prepared by spraying on the carbon paper with the machine. In our study, the Pt-Sn/C catalyst appears to be a promising methanol tolerant catalyst with activity towards the ORR in the DMFC

Electrochemistry and electrophoresis of mercury cysteine and ditizone complexes

Thesis (MSc (Chemistry and Polymer Science))--Stellenbosch University, 2008.There are various mercury species in the environment and their toxicity and availability relies on their chemical form and oxidation states. Inorganic and organic mercury is found to co-exist in water and body tissue of some organisms. Among them inorganic mercury has a lower toxicity than the organic mercury. Methyl mercury (CH3Hg+) is the most toxic species found in the environment because it can enter the food chain accumulating and contaminating humans. Hence the total mercury concentration does not reflect the important information and thus the needs for the development of methods for the simultaneously separating and determination of mercury species. A study of the electrochemistry of mercury and organo mercury complexes with cysteine and dithizone indicated the formation of stable complexes, which can be utilized for the determination of the species in environmental matrices. Cyclic voltammetry is used to determine the electrochemical properties of the complexes. A technique based on capillary electrophoresis and amperometric detection (CE-AD) has been developed for the speciation of mercury. This technique has the capability to detect mercury species that are electrochemically active. Using capillary electrophoresis in combination with electrochemical detection makes speciation of the complexes possible at lower than normal concentrations. For CE-AD the detection limits were 0.005 μg/L for Hg2+ and 0.4 μg/L for MeHg+. These detection sensitivities are attractive for environmental monitoring