Philosophiae Doctor - PhD / The direct methanol fuel cell or DMFC is emerging as a promising alternative energy source for many applications. Developed and developing countries, through research, are fast seeking a cheap and stable supply of energy for an ever-increasing number of energy-consuming portable devices. The research focus is to have DMFCs meeet this need at an affordable cost is problematic. There are means and ways of making this a reality as the DMFC is found to be complementary to secondary batteries when used as a trickle charger, full charger, or in some other hybrid fuel cell combination. The core functioning component is a catalyst containing MEA, where when pure platinum is used, carbon monoxide is the thermodynamic sink and poisons by preventing further reactions at catalytic sites decreasing the life span of the catalyst if the CO is not removed. Research has shown that the bi-functional mechanism of a platinum-ruthenium catalyst is best because methanol dehydrogenates best on platinumand water dehydrogenation is best facilitated on ruthenium. It is also evident that the addition of other metals to that of PtRu/C can make the catalyst more effective and effective and increase the life span even further. In addition to this, my research has attempted to reduce catalyst cost for DMFCs by developing a low-cost manufacturing technique for catalysts, identify potential non-noblel, less expensive metallic systems to form binary, ternary and quarternary catalysts. / South Africa

>Magister Scientiae - MSc / Fuel cells are widely considered to be efficient and non-polluting power source offering much higher energy density. This study is aimed at developing oxygen reduction reactions (ORR) catalysts with reduced platinum (Pt) loading. In order to achieve this aim, monometallic Pd and Pt nanostructured catalysts were electrodeposited on a substrate (carbon paper) by surface limited redox replacement using electrochemical atomic layer deposition (ECALD) technique. Pd:Pt bimetallic nanocatalysts were also deposited on carbon paper. Pd:Pt ratios were (1:1, 2.1 and 3:1). The prepared mono and bimetallic catalysts were characterized using electrochemical methods for the ORR in acid electrolyte. The electrochemical characterization of these catalysts includes: Cyclic Voltammetry (CV) and linear sweep voltammetry (LSV). The physical characterization includes: scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) for Morphology and elemental composition, respectively. The deposition of copper (Cu) on carbon paper was done by applying a potential of -0.05 V at 60s, 90s and 120s. 8x cycles of Pt or Pd showed better electrochemical activity towards hydrogen oxidation reaction. Multiples of eight were used in this work to deposit Pt: Pd binary catalyst. Cyclic voltammetry showed high electroactive surface area for Pt24Pd24/Carbon-paper while LSV showed high current density and positive onset potential. HRSEM also displayed small particle size compared to other Pt:Pd ratios.

Hydrogen is seen as the green fuel of the future for the aeronautical sector allowing to reduce the carbon footprint of commercial aviation. It is well established that the release of carbon emissions triggers global warming. Aviation, like many other industries, must reduce them. This study aims to integrate cryogenic hydrogen storage onboard an existing aircraft and study two different propulsion systems, namely hydrogen combustion and fuel cells. A cryogenic tank was modelled and then designed to fit in the fuselage of an A321. Two configurations were studied, one consisting of one tank at the rear and the other with two tanks, one at the front and one at the aft. The result showed a significant variation of the centre of gravity for the rear tank configuration, whether the airplane is empty or with payload. Among the two propulsion systems investigated, hydrogen combustion requires less of a technological leap than hydrogen fuel cell aircraft. The limitation would be the range due to the lack of volume onboard the aircraft to store the hydrogen fuel. But this new type of propulsion could lay the groundwork for future fuel cell aircraft. The fuel cells technology still needs to improve its power density to compete with current engines but would o er more efficient aircraft and therefore greater range.

This master’s thesis focuses on optimization of electrode configuration in combination with a polymer membrane (MEA - Membrane Electrode Assembly) in terms of material and technology. The main goal was to create a functional measurement of MEA structures with three different types of carbon materials. The theoretical part focuses on the physical and chemical properties of low-temperature fuel cells with polymer membrane. The experimental section describes the manufacture of catalytic materials with different types of carbon and various contents platinum. Produced by electrode materials were investigated by cyclic voltammetry. The next step was to manufacture MEA structures and characteristics of VA measurement using a digitally controlled load in the experimental fuel cell Quintech.

One contemporary issue experienced worldwide is the climate change due to the combustion of fossil fuels. Microbial Electrochemical Systems pose as an alternative for energy generation. In this technology, microorganisms are primarily responsible for electricity production. To improve the performance it is reasonable to think that bacteria from diverse environments, such as the brine pools of the Red Sea, can be utilized in these systems. Samples from three brine pools: Atlantis II, Valdivia, and Kebrit Deeps, were analyzed using Microbial Electrochemical Cells, with a poised potential at +0.2 V (vs. Ag/AgCl) and acetate as electron donor, to evaluate the exoelectrogenic activity by the present microorganisms. Only samples from Valdivia Deep were able to produce a noticeable current of 6 A/m2. This result, along with acetate consumption and changes on the redox activity measured with cyclic voltammetry, provides arguments to con rm the presence of exoelectrogenic bacteria in this environment. Further characterization using microscopy and molecular biology techniques is required, to obtain the most amount of information about these microorganisms and their potential use in bioelectrochemical technologies.

>Magister Scientiae - MSc / Anode catalysts are one of the key components of direct alcohol fuel cells (DAFCs). They play a huge role in the alcohol oxidation reaction (AOR) that occurs on the anode side. Palladium (Pd) supported on carbon material has been reported to have good catalytic activity towards alcohol oxidation reactions. Better stability and activity has been reported for catalysts supported on conductive polymers like polypyrrole (PPy) when compared to traditional carbon support material. This study investigated the effect of support materials on Pd and PdCo electro-catalysts while concurrently determining the support material that can improve the activity and stability of Pd and PdCo electro-catalysts used as direct alcohol fuel cells catalysts. All Pd and PdCo catalysts supported onPPy (prepared using oxidative polymerization method), reduced graphene oxide (rGO) and prepared using modified Hammers method and multi-walled carbon nanotubes and pre-treated by acid. All the catalysts were synthesized using the modified polyol method.

>Magister Scientiae - MSc / Polymer electrolyte membrane fuel cells (PEMFC) are in the forefront of energy production and have drawn a great deal of attention in both fundamental and application in recent years. It is a promising energy system used in commercialized electric vehicles presenting with the following advantages: low-temperature operation, high power density (40%–60%), nearly zero pollutants compared to conventional internal combustion gasoline vehicles, simple structure, and so on. There are, however, two major obstacles which obstruct PMFCs pathway to commercialization— durability and cost. Recent advances in PEMFC systems showed the most common fuel cell catalysts to be Platinum (Pt) (or platinum alloys) supported by high surface carbon in both the cathode and anode. However, carbon is very susceptible to corrosion and results in lower durability of Pt supported catalysts.

Thesis advisor: Chia-Kuang Tsung / Heterogeneous catalysis is a critical field for chemical industry processes, energy applications, and transportation, to name a few. In all avenues, control over the activity and selectivity towards specific products are of extreme importance. Generally, two separate methods can be utilized for controlling the active surface areas; a below and above the surface approach. In this dissertation, both approaches will be addressed, first starting with controlling the active sites from a below approach and moving towards control through sieving and gating effects above the surface. For the first part half, the control of the product selectivity is controlled by finely tuning the atomic structures of nanoparticle catalysts, mainly Au-Pd, Pd-Ni-Pt, and Pd Ni3Pt octahedral and cubic nanoparticle catalysts. Through these shaped core-shell, occasionally referred to as core@shell, particles the shape is maintained in order to expose and study certain crystal facets in order to obtain a more open or closed series of active sites. With the core shell particles, the interior core particle (Au and Pd) is used for the overall shape but also to expansively/compressively strain the outer shell layer. By straining the surface, the surface electronic structure is altered, by raising or lowering the d-band structure, allowing for reactants to adsorb more or less strongly as well as adsorb on different surface sites. For the below the surface projects, the synthesized nanoparticle catalyst are used for electrochemical oxidation reactions, such as ethanol and methanol oxidation, in order to study the effect of the core and shell layers on initial activity, metal migration during cycling, as well as particle stability and activity using different crystal structures. In particular, the use of core shell, alloyed, and intermetallic (ordered alloys) particles are studied in more detail. In the second half of this dissertation, control of the selectivity will be explored from the top down approach; in particular the use of metal organic framework (MOF) will be utilized. MOF, with its inherent size selective properties due to caging effects from the chosen linkers and nodes, is used to coat the surface of catalysts for gas, liquid, and electrochemical catalysis. By using nanoparticle catalyst, the use of MOF, more explicitly the robust zirconium based UiO-66, as a crystalline capping agent is first explored. By incorporating both the nanoparticle and UiO-66 amino functionalized precursors in the synthesis, the nanoparticles are formed first and followed by coating in UiO-66-NH2, where the amino group acts as an anchor, completely coating the particles. The full coating is tested through size selective alkene hydrogenations with the NP surface further tested by liquid phase selective aldehyde hydrogenations; the UiO-66-NH2 pores help to guide the reactant molecule in a particular orientation for the carbonyl to interact rather than the unsaturated C=C bond. This approach is taken for more complex hybrid structures for electrochemical proton exchange membrane fuel cell (PEMFC) conditions. Through the gating effects, the UiO-66 blocks the Pt surface active sites from poisonous sulfonate groups off of the ionomer membrane while simultaneously preventing aggregation and leaching of Pt atoms during electrochemical working conditions. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Pentafluorosulfur (VI) bromide (SF5Br) adds to olefins of the form CX2=CX2, where X= H or F, with the pentafluorosulfur group usually adding to the carbon with more hydrogens attached to it. This series of compounds was used in an attempt to prepare the corresponding sulfonic acid hydrates of the general formula SF5CX2CX2SO3H·nH2O, in order to have these compounds tested as possible fuel cell electrolytes. The reaction scheme involved reflux of the SF5Br adduct with an equimolar amount of sodium sulfite in 50% ethanol for two days, followed by acidification of the recovered solid material using HCl or H2SO4.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17890号 / 工博第3799号 / 新制||工||1581(附属図書館) / 30710 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM