This dissertation the syntheses of Pt-based binary and ternary alloy electrocatalysts using the transition metals of Co and Ni are presented. These electrocatalysts were synthesised by an impregnation-reduction procedure at high temperature whereby Pt supported on carbon, (Pt/C (40 percent), was impregnated with the various metal and mixtures thereof and reduced at high temperatures in a H2 atmosphere. The procedure was also designed in such a way so as to prevent the oxidation of the support material (carbon black) during the alloy formation. The resultant nanoparticles (9-12 nm) of Pt3Co/C, Pt3Ni/C and Pt3Co0.5Ni0.5/C were also subjected to a post treatment procedure by acid washing (denoted AW) to produce electrocatalysts of Pt3Co/C-AW, Pt3Ni/C-AW and Pt3Co0.5Ni0.5/C-AW to study the effect of acid treatment on these electrocatalysts. The synthesised electrocatalysts were then characterised by a number of physical and electrochemical techniques and compared to that of commercial Pt/C (Pt/C-JM, HiSpec 4000) as well as Pt/C catalysts (Pt/C-900 and Pt/C-900-AW) treated under the same conditions used for the alloy synthesis. The electrocatalysts were then used to fabricate MEAs that were loaded into commercial single test cells and characterised by means of polarisation curves and Electrochemical Impedance Spectroscopy (EIS). The extensive physical characterisation included Powder X-Ray Diffraction (PXRD) analysis, Transmission Electron Microscopy (TEM), elemental analysis by Energy Dispersive Spectroscopy (EDS) and metal loading by Thermo-Gravimetric Analysis (TGA). These studies showed that Pt-based alloy electrocatalysts were successfully synthesised with particle sizes ranging from 9 - 12 nm, within their respective atomic ratios and whereby no significant loss of carbon support occurred. This indicated that significant sintering or electrocatalyst particles occurred when compared to that of the starting Pt/C catalyst (3 – 4 nm). From the combined results of the physical characterisation procedures, it was also shown that leaching as a result of acid washing was catalyst dependent with Ni containing catalysts showing a significant degree of leaching compared to that of Co containing catalysts. Electrochemical characterisation in terms of Electrochemical Active Surface Area (ECSA) by Cyclic Voltammetry (CV) and ORR activity by Rotating Disc Electrode (RDE) analysis revealed that a significant decrease in the ECSA resulted from the increase in particle size and this had a major influence on the ORR activity. Furthermore it was found that a significant improvement in the ORR activity was achieved by the synthesis of Pt-based alloys. It was also found that catalytic properties of the acid washed electrocatalysts were substantially different from that of non-acid washed electrocatalysts. The experimental data confirmed that it was possibly to achieve better catalytic performance as compared to that of Pt/C at a lower material cost when Pt is alloyed with base transition metals. The trend observed from the ORR activity studies by RDE was successfully repeated in the in-situ fuel cell testing in terms of mass activity of the electrocatalysts. Of the electrocatalysts studied under „real‟ fuel cell conditions Pt/C-JM had the best performance compared to the others, with the ternary Pt3Co0.5Ni0.5/C showing better catalytic performance compared to the Pt3Co/C electrocatalyst. This was found to be due to a higher charge transfer resistance observed in Pt3Co/C as compared to that of Pt3Co0.5Ni0.5/C which was similar than that of the commercial Pt/C-JM catalyst with both Pt3Co/C and Pt3Co0.5Ni0.5/C-AW having similar but higher ohmic resistances than that of Pt/C-JM as determined by electrochemical impedance spectroscopy. The results showed that a great potential exist to improve the catalytic performance of low temperature PEM fuel electrocatalysts at a reduced cost as compared to that of pure Pt provided a method of controlling the particle size was established.

Polymer electrolyte membrane fuel cell (PEMFC) stacks require sealing around the perimeter of the cells to prevent the gases inside the cell from leaking. Elastomeric materials are commonly used for this purpose. The overall performance and durability of the fuel cell is heavily dependent on the long-term stability of the gasket. In this study, the degradation of three elastomeric gasket materials (silicone rubber, commercial EPDM and a developed EPDM 2 compound) in an accelerated ageing environment was investigated. The change in properties and structure of a silicone rubber gasket caused by use in a real fuel cell was studied and compared to the changes in the same silicone rubber gasket material brought about by accelerated aging. The accelerated aging conditions were chosen to relate to the PEM fuel cell environment, but with more extreme conditions of elevated temperature (140°C) and greater acidity. Three accelerated ageing media were used. The first one was dilute sulphuric acid solution with the pH values of 1, 2 and 4. Secondly, Nafion® membrane suspended in water was used for accelerated ageing at a pH 3 to 4. Finally, diluted trifluoroacetic acid (TFA) solution of pH 3.3 was chosen. Weight change and the tensile properties of the aged gasket samples were measured. In addition, compression set behaviour of the elastomeric seal materials was investigated in order to evaluate their potential sealing performance in PEM fuel cells. The results showed that acid hydrolysis was the most likely mechanism of silicone rubber degradation and that similar degradation occurred under both real fuel cell and accelerated aging conditions. The effect of TFA solution on silicone rubber was more aggressive than sulphuric acid and Nafion® solutions with the same acidity (pH value) suggesting that TFA accelerated the acid hydrolysis of silicone rubber. In addition, acid ageing in all three acidic solutions caused visible surface damage and a significant decrease in tensile strength of the silicone rubber material, but did not significantly affect the EPDM materials. EPDM 2 compound had a desirable (low) compression set value which was similar to silicone rubber and much better than the commercial EPDM. It also showed a very good performance in the fuel cell test rig conforming that it a potential replacement for silicone rubber in PEMFCs.

Higher temperature (~ 200°C) operation for proton exchange membrane (PEM) fuel cells would have several advantages including enhanced electrochemical kinetics, useful heat recovery, and improved catalyst tolerance for contaminants. Conventional perfluorosulfonic acid membranes (PFSA), such as Nafion show a dramatic decrease in proton conductivity at temperatures above 80°C. For this reason, there has been an increasing effort toward the development of stable, higher temperature membranes with acceptable proton conductivity. This work is directed toward the development of Nafion free membranes for direct hydrocarbon PEM fuel cells containing zirconium phosphate as the proton conductor component. Hence, composite membranes composed of zirconium-phosphate (ZrP), a solid proton conductor, which was precipitated within the voids of a porous polytetraflouroethylene (PTFE) support were synthesized. Amorphous-like zirconium phosphate (ZrP) powder was synthesized in this work. ZrP was prepared by precipitation at room temperature via reaction of ZrOCl2 with H3PO4 aqueous solutions. The proton conduction properties of ZrP powder were studied under the processing conditions found in direct hydrocarbon fuel cell. Our experimental results showed that the ZrP powder processed at 200°C possess a proton conductivity that is greater by one order of magnitude than the oven-dried samples at 70°C. Thereby, it was possible to avoid the normal decrease in conductivity with increasing temperature by having sufficient water in the vapor phase. This thesis reports the first synthesis of composite ZrP/PTFE/Glycerol (GLY) membranes. Glycerol (GLY) was introduced into the pores of PTFE with the ZrP proton conductive material using the successive wetting/drying technique. These membranes had reasonable values of proton conductivities (0.045 S cm-1), approaching that of Nafion (0.1 S cm-1) at room temperature. Samples of these composite membranes were processed at the inlet conditions of a propane fuel cell, at 200°C. Experimental results showed that the proton conductivity remained almost unchanged. This thesis also describes and reports the first synthesis of sulphur “S” or silicon, Si–modified zirconium phosphate (ZrP), porous polytetrafluoethylene (PTFE) and, glycerol (GLY) composite membranes. It was aimed at the substitution of a minor amount of phosphorus “P” in the ZrP by (S or Si) in the ZrP to modify the proton conduction properties. The modification was performed by adding a certain amount of silicic acid or sulphuric acid into phosphoric acid then proceeding with the precipitation in situ. A high proton conductivity, of 0.073 S cm-1,i.e. 73% of that of Nafion, was observed for the Si–ZrP/PTFE/GLY composite membrane.

Direct ethanol fuel cells have been shown to be a good alternative to internal combustion engines in order to reduce the CO2 emissions. In this study, Pd and Pd-based nanocatalysts were deposited on various supports (carbon black, graphene, SnO2, CeO2, TiO2, TiO2 nanotubes and SnO2/TiO2 nanotubes) and their effects on the catalytic properties of the deposited metal for ethanol oxidation in alkaline media are studied. These modifications to the catalytic systems have shown to cause an increase in the reaction rate at the surface of the catalyst and to reduce the overpotential of the ethanol oxidation reaction. Two different promotion mechanisms have been identified. Firstly, the supply of OH- ions at the metal-support interface facilitates the oxidation of adsorbed molecules on neighbouring Pd sites. Secondly, an increase in electron density of Pd nanoparticles with increasing support reducibility modifies the adsorption strength of ethanol and its oxidation intermediates.

The work in this thesis addresses the synthesis and characterization of porous carbon substrates, and their electrochemical and fuel cell evaluation. The approach involves using porous carbon materials of different pore characteristics as electrocatalyst materials for use as cathode catalyst substrates in direct methanol fuel cells (DMFC). In this work, a porous carbon, known as carbonaceous Celatom or C-Celatom, was prepared by template synthesis using a widely abundant, inexpensive macroporous silica structure diatomaceous earth (Celatom FW-80). Ordered mesoporous carbon CMK-3 was also produced by template synthesis of mesoporous silica SBA-15. Scanning electron microscopy (SEM) and x-ray diffraction (XRD) were used to confirm the synthesis of the desired carbon structures. Three different platinum deposition techniques were investigated for electrocatalyst synthesis, an incipient wetness technique, as ethylene glycol reduction technique, and an alkoxide reduction technique. Transmission electron microscopy (TEM) and SEM analysis of the catalysts formed using the incipient wetness and ethylene glycol techniques showed that the synthesized catalysts were not suitable for fuel cell use. Optimization of the alkoxide reduction technique resulted in a deposition technique that resulted in a well-dispersed catalyst with small, uniform particle sizes (2.1-3.1 nm). The synthesized electrocatalysts were evaluated electrochemically and found to have high electrochemically active surface areas (ESA) of 33.38 m2 g-1 for Pt/Vulcan XC-72, 22.45 m2 g-1 for Pt/CMK-3 and 20.51 m2 g-1 for Pt/C-Celatom. The oxygen reduction (ORR) activity was evaluated by linear sweep voltammetry(LSV). The Pt/C-Celatom exhibited the greatest activity towards the oxygen reduction reaction, and the greatest number of active sites for the ORR. Assessment of the material by electrochemical impedance spectroscopy (EIS) also showed that an MEA with C-Celatom as the cathode catalyst has the lowest combines charge transfer and mass transport resistance. Single cell DMFC testing was carried out with each of the experimental substrates. The synthesized catalysts demonstrated high performance over a range of temperatures and feed molarity concentrations. The C-Celatom MEA exhibited the greatest power output of the synthesized catalysts for low molarity operation, with peak power densities of 25.8 and 32.6 mW cm-2 with 0.5M and 1M feed respectively.

The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI) zwitterionic polymers as electrolytes in polymer electrolyte membrane (PEM) fuel cells. The proposed diazonium PFSI zwitterionic polymers are expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency in electrodes for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homoplymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride and coupling reaction with 4-nitrobenzene sulfonyl amide have been carried out successfully in the lab. All the intermediate chemicals are characterized by 1H NMR, 19F NMR and IR.

No description available.

Water electrolysis conjugated with renewable energy sources potentially realizes a sustainable society. Although the current electrolyzers operate at extreme pH to maximize the electrolysis efficiency, near-neutral pH conditions may optimize the overall system operation when conjugated with renewable energy sources. In this context, a study on the electrolysis in the mild conditions is essential. The dissertation investigates the water electrolysis in various conditions, with a particular focus placed on milder conditions, to rationalize and improve its performance. Microkinetic analysis was performed for the cathodic half-reaction in conjugation with mass transport evaluation using various electrode materials. The analysis revealed a significant universal influence of electrolyte properties on the reaction performances at near-neutral pH. Investigation of the associated electrolyte properties (ion size, viscosity and activity/fugacity) rationally optimized the reaction conditions. Together with the separately performed studies on the anodic half-reaction and system configurations, the finding was successfully transferred to electrocatalytic and solar-driven water splitting systems. The presented herein is a fundamental yet crucial aspect of water electrolysis, which can advance the water electrolysis for the future.

No description available.

As the amount of data centers continues to increase, their electricity consumption and emissions are being reviewed. The current backup solution is a conventional diesel generator running on fossil fuels. As part of climate goals to reduce carbon emissions, renewable energy sources like fuel cells running on hydrogen are being considered. The following degree project aims to analyse the impact of replacing a fossil-powered backup power system with fuel cells as well as providing insights into which parameters affect the economic analysis the most. Current studies, reports and websites were used to gather a better understanding of fuel cell systems and their key components. The calculations were carried out using values obtained from literature which then were used for simulations in Excel. The results indicated a net profit for the proposed fuel cell system during the expected lifetime. A proton exchange membrane fuel cell (PEMFC) functions very similarly to a diesel generator while reducing emissions. While the operating costs for the conceptual FC system are lower, the initial investment is much more expensive compared to the diesel system. Even though the economic investment yields a negative profit, large carbon dioxide savings are made. To give a better understanding of how different aspects impact the economics a sensitivity analysis was also carried out. While the current results show that the investment is not feasible, many of the parameters analysed in the sensitivity analysis indicate a more hopeful future forecast.