ABSTRACT. Different IrO2 electrodes in which the molar percentage of platinum (Pt) varies from 0 %mol Pt to 100 %mol Pt were prepared on titanium (Ti) substrate by thermal decomposition techniques. The electrodes were characterized physically (SEM, XPS) and electrochemically and then applied to methanol oxidation. The SEM micrographs indicated that the electrodes present different morphologies depending on the amount of platinum in the deposit and the cracks observed on the 0 %mol Pt electrode diminish in size tending to a compact and rough surface for 70 %mol Pt electrode. XPS results indicate good quality of the coating layer deposited on the titanium substrate. The voltammetric investigations in the supporting electrolyte indicate that the electrodes with low amount of platinum (less than 10 %mol Pt) behave as pure IrO2. But in the case of electrodes containing more than 40 %mol Pt, the voltammograms are like that of platinum. Electrocatalytic activity towards methanol oxidation was observed with the electrodes containing high amount of platinum. Its oxidation begins at a potential of about 210 mV lower on such electrodes than the pure platinum electrode (100 %mol Pt). But for electrode containing low quantity of Pt, the surface of the coating is essentially composed of IrO2 and methanol oxidation occurs in the domain of water decomposition solely. The increase of the electrocatalytic behaviour of the electrodes containing high amount of Pt towards methanol oxidation is due to the bifunctional behaviour of the electrodes.

The mixed coupled xPtOy-(100-x)IrO2 electrodes (x = 0, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100) were thermally prepared at 450 °C on titanium supports. The prepared electrodes were firstly physically characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Afterwards, electrochemical characteri­zations were performed by voltammetric (cyclic and linear) methods in different electrolyte media (KOH and HClO4). It is shown that the prepared electrodes are composed by both PtOy (platinum and platinum oxide) and IrO2 (iridium dioxide). For xPtOy-(100-x)IrO2 electrodes having higher content of IrO2, more surface cracks and pores are formed, defining a higher surface area with more active sites. Higher surface area due to presence of both PtOy and IrO2, is for xPtOy-(100-x)IrO2 electrodes in 1 M KOH solution confirmed by cyclic voltammetry at potentials of the oxide layer region. For all prepared electrodes, voltammetric charges were found higher than for PtOy, while the highest voltammetric charge is observed for the mixed 40PtOy-60IrO2 (x = 40) electrode. The Tafel slopes for oxygen evolution reaction (OER) in either basic (0.1 M KOH) or acid (0.1 M HClO4) media were determined from measured linear voltammograms corrected for the ohmic drop. The values of Tafel slopes for OER at PtOy, 90PtOy-10IrO2 and IrO2 in basic medium are 122, 55 and 40 mV dec-1, respectively. For other mixed electrodes, Tafel slopes of 40 mV dec-1 were obtained. Although proceeding by different OER mechanism, similar values of Tafel slopes were obtained in acid medium, i.e., Tafel slopes of 120, 60 and 39 mV dec-1 were obtained for PtOy, 90PtOy-10IrO2 and IrO2, and 40 mV dec-1 for other mixed electrodes. The analysis of Tafel slope values showed that OER is more rapid on coupled mixed electrodes than on pure PtOy. For mixed xPtOy-(100-x)IrO2 electrodes, OER is more rapid when the molar percent of PtOy meets the following condition: 0 ˂ x ≤ 80. This study also showed that the mixed coupled electrodes are more electro­cata­lytically active for OER than either PtOy or IrO2 in these two media.