A comparative study between Pt and Rh for the electro-oxidation of aqueous SO₂ and other model electrochemical reactions

MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The ever increasing demand for a clean and renewable energy source has stimulated research for alternatives for the use of fossil fuels, which contribute significantly to global warming. The SO2 oxidation reaction was studied for production of hydrogen as a clean and renewable energy carrier. This reaction occurs at a lower standard electrode potential (0.158 V vs. SHE) than normal water electrolysis (1.23 V vs. SHE). This is a theoretical indication that the SO2 oxidation reaction has possible potential when compared to normal water electrolysis, since hydrogen production may occur at lower potentials and therefore lower cost. Rh was compared with Pt for the SO2 oxidation reaction since little research has been done on this catalyst and many studies exist in which Pt was used as catalyst. The oxygen reduction reaction and ethanol oxidation reaction were also included in this study to create a foundation for the catalysts studied, since the SO2 oxidation reaction is complicated by different adsorbed species that can form according to various mechanisms. The electrochemical techniques employed in this study to characterize the catalysts included cyclic voltammetry from which onset potentials and limiting current densities were determined, as well as from which some qualitative analysis was done. Linear polarization experiments were used during rotating disk electrode studies from which Levich and Koutecky-Levich analyses were done and the number of electrons transferred calculated and compared between the two catalysts. From the Koutecky-Levich analysis the kinetic current density was also obtained for use in Tafel analysis for further comparison between catalysts. It was found that Rh showed good behaviour for the oxygen reduction reaction when compared to Pt with similar onset potentials and limiting current densities. From Levich analysis it was concluded that both catalysts achieved diffusion limitation at high overpotentials. However, from the calculated number of electrons transferred it was evident that a difference in mechanism existed between catalysts and that the mechanism for both changed in the potential range studied, which is confirmed by the Tafel slopes. For the ethanol oxidation reaction it was shown that Rh exhibited very low catalytic activity in comparison with Pt. However, it was concluded from cyclic voltammetry and rotating disk electrode studies that more adsorbed species were present on the surface of Rh than on Pt. These results confirmed the possibility of using Rh as a co-catalyst together with Pt since it was shown from rotating disk electrode studies that low adsorption of ethanol and its oxidation products caused species to be transported away from the surface of the electrode during rotation. For the SO2 oxidation reaction it was found that Rh exhibited very poor catalytic activity together with being very susceptible to poisoning by adsorbed species. Pt showed very good behaviour, which corresponded well with what had been observed in literature. Levich analysis revealed that Pt did not exhibit diffusion limitation and Koutecky-Levich analysis revealed that a 2 electron reaction occurred on Pt, which corresponds with the SO2 oxidation reaction during which 2 electrons are transferred. It was, therefore, shown that Rh could exhibit good behaviour and act as a suitable catalyst in certain circumstances. However, for the SO2 oxidation reaction, which was the main focus of this study it was shown that Rh is not a suitable catalyst, either alone or as co-catalyst.

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