Browsing by Author "Fortuin, Adrian Charles"

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    Development of a semi–empirical reaction kinetic model for PEM fuel cells
    (2013) Fortuin, Adrian Charles; Conrad, Olaf; Levecque, Pieter B J
    In the drive to more sustainable energy production, polymer electrolyte fuel cells (PEFC) have been at the pinnacle of global research. One of the major drawbacks of PEFCs is therequirement for expensive noble metal catalysts (platinum and ruthenium). Furthermore 75% of the overpotential losses at the cathode are due to the activation of the oxygen reduction reaction (ORR). To reduce the platinum content requirements and understand the cause of the large overpotential of the ORR, a fundamental understanding of the reaction mechanism and the manner in which it proceeds under different operatingconditions is required. Presently, there still remains a large debate in literature around the mechanism followed by the ORR.This study developed a kinetic model from conventional kinetic isotherms and it is proposed that an associative adsorption mechanism occurs at a low overpotential resulting in the dissociation of the hydroperoxyl species determining the rate of the ORR at the cathode of the PEFC. In order to explain the above phenomena a kinetic model was developed, based on the Eley-Rideal mechanism. Furthermore, experiments were conducted at different oxygen partial pressures and low potentials whereby the associative mechanism is believed to dominate. Under these conditions linear sweep voltammograms were recorded. Regression of the derived kinetic model, by using the values for oxygen partial pressure, applied overpotential and kinetic current allowed for the determination of the kinetic constant of a polycrystalline platinum catalyst for ORR.
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    Towards identifying platinum anchor sites on carbon via a model electrochemical system
    (2018) Fortuin, Adrian Charles; Levecque, Pieter; Scherer, Günther
    The interaction between Pt and its carbon support was investigated by a model electrochemical system. This entailed aggressively oxidising a two-dimensional carbon substrate, i.e. highly orientated pyrolytic graphite (HOPG) and mirror finish graphite (MFG) quartz crystal, to incorporate oxygen terminated groups into the graphitic matrix. This study focusses on potential cycling to determine the mobility of Pt across these carbon surfaces and the effect of the Pt anchoring to carbon on the electrocatalyst durability. This work incorporates both a conventional three electrode electrochemical setup and the use of the electrochemical quartz crystal nano-balance (EQCN). The objectives of this study were to better understand the Pt mobility across the carbon substrate surface and to gain insight into the solid-liquid interface of Pt dissolution due to potential cycling. Initial results on HOPG as discussed in chapter 2, indicated minimal Pt dissolution of between 13% and 15% of total electrochemical active surface area loss. These results, however, did not provide adequate evidence to conclusively determine the extent of Pt mobility on the carbon surface and the effect of oxygen terminated groups in hindering Pt dissolution. In order to gain a more thorough understanding of the Pt dissolution processes, the use of the EQCN technique was utilised. Firstly, it was shown that the mirror finished graphite quartz crystals used in the EQCN technique, are qualitatively comparable to the electrochemical measurements recorded with the HOPG samples. Secondly, potential cycling under the same conditions as HOPG produced similar electrochemical results. The frequency response curves from the EQCN yielded the most promising results. This study showed, qualitatively, that the surface of Pt is non-monotonic, and that the surface charge changes with increased potential cycling. Pt/MFG-A had consistent frequency responses over the entire potential range during Pt dissolution, thus, with the above understanding of surface charge, it is concluded that acid treated carbon substrates show a stronger affinity for Pt anchoring.