Platinum negative potential limit

Figure 4.8 shows the potential windows obtained at a bright platinum electrode, based on the Fc+/Fc (solvent-independent) potential scale. Because of the overpotentials, the window in water is 3.9 V, which is much wider than the thermodynamic value (2.06 V). The windows for other solvents also contain some overpotentials for the reduction and the oxidation of solvents. However, the general tendency is that the negative potential limit expands to more negative values with the decrease in solvent acidity, while the positive potential limit expands to more positive values with the decrease in solvent basicity. This means that solvents of weak acidity are difficult to reduce, while those of weak basicity are difficult to oxidize. This is in accordance with the fact that the LUMO and HOMO of solvent molecules are linearly related with the AN and DN, respectively, of solvents [8]. 

With regard to electrode material, it can be seen (Tables 4 and 5) that cathodic limits on mercury are displaced by a few tenths of a volt to more negative potentials than on platinum. On the anodic side, the number of practically useful electrode materials is limited to noble metals and different types of carbon one case (anodic limit of pyridine nos. 35 and 36) shows that the anodic limit is lower on graphite than on platinum, and this seems to be a general trend for the comparison of carbon based anode materials, except possibly for vitreous carbon (Table 5) and bright (smooth, polished or shiny) platinum. 

The peak around —0.38 V versus mercury/mercurous sulfate reference electrode (MSE), during the negative sweep, is associated to gold species whereas the one at —0.8 V versus MSE corresponds to platinum species. For pure catalysts, with an upper potential limit of +0.25 V versus MSE, the charge values of 493 and 543 pC cm-2 were obtained for platinum and gold, respectively (Figure 21.7).43,44 The atomic content of the Pt-Au nanoparticles can be deduced as follows ... 

Water or protons ai e easily reduced at a platinum electrode, limiting tlie available negative potential range to about —0.1 V versus SCE. 

The potential limits are particularly dependent on the eluent pH. In principle, more negative potentials may be applied in alkaline solution than in acidic solution and, conversely, in acidic solution more positive potentials may be selected than in alkaline solution. For oxidation reactions at high positive potentials, glassy carbon and platinum electrodes are suited reduction reactions at very negative potentials can be performed at glassy carbon, silver, and gold electrodes. 

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